Aliphatic diol-based polycarbonates, method of making, and articles formed therefrom

ABSTRACT

The above-described and other deficiencies of the art are met by a method of making a polycarbonate polymer comprising isosorbide carbonate units, comprising melt reacting a dihydroxy compound comprising an isosorbide of the general formula (2 a ): 
     
       
         
         
             
             
         
       
         
         
           
             and an activated carbonate, in the presence of a catalyst consisting essentially of a sodium salt capable of providing a hydroxide ion, wherein the polycarbonate polymer comprises greater than or equal to 50 mol % isosorbide carbonate units, and wherein the polycarbonate polymer has a Mw of greater than or equal to about 40,000 g/mol as determined by gel-permeation chromatography relative to polystyrene standards. Polycarbonates comprising the isosorbide carbonate unit, including isosorbide homopolycarbonate and an isosorbide-based polyester-polycarbonate, are also disclosed, as are a thermoplastic composition and an article including the isosorbide-based polycarbonate polymer.

BACKGROUND

This disclosure relates to polycarbonates comprising aliphatic diols,and in particular to isosorbide-based polycarbonates, and methods ofmanufacture thereof.

Polycarbonate homopolymers and copolymers of aliphatic diols,particularly isosorbides (i.e., 2,6-dioxabicyclo[3.3.0]octan-4,8-dioland isomers), are of great interest to the chemical industry becausesuch aliphatic diols can be produced from renewable resources, namelysugars, rather than from petroleum feed stocks as for most presentlyused bisphenol monomers.

However, the homo- or copolycarbonate incorporating isosorbide needs tobe of sufficiently high molecular weight to have properties of practicalimportance. There have been several previous attempts to producepolycarbonates from isosorbide, but each of these attempts has had itsdifficulties, and therefore at present, such polycarbonates are notproduced commercially. For instance, the primary method for preparingpolycarbonates generally uses interfacial polymerization in methylenechloride/water using phosgene and alkali. In this method, one or morediols (e.g., bisphenols) in an aqueous alkaline solution are mixedthoroughly, with stirring, in methylene chloride or other suitablehalogenated solvent and can be converted to high molecular weightpolycarbonates by introducing phosgene. However, this method is notsuitable for preparing homopolycarbonate derived from isosorbide becausethe isosorbide solubility in water is too high, impeding the interphasetransfer, and its acidity too low to proceed at an adequate rate in pHranges suitable for interfacial phosgenation.

Isosorbide polycarbonate homopolymer has been prepared by solutionpolycondensation in pyridine containing solvent mixtures at lowtemperatures. It has also been prepared by converting isosorbide to thebischloroformate and polymerized by interfacial polymerization. Thepolymer obtained exhibited a Tg of 144 to 155° C. (See e.g., Angew.Makromol. Chem, 1993, vol. 199, p. 191; U.S. Pat. No. 4,506,066;Macromolecules 1996, vol. 29, p. 8077). Attempts have also been made toprepare copolycarbonates of isosorbide with bisphenol A by interfacialmethod in an alkaline water/methylene chloride mixture with phosgene.Only bisphenol A polycarbonate was obtained and no incorporation ofisosorbide was observed (U.S. Pat. No. 4,506,066).

An alternative method of synthesizing polycarbonates is by use of meltpolymerization. The reaction of a bisphenol with a source of carbonateunits such as diphenyl carbonate (DPC) in the presence of a catalyst andthe absence of solvent are typical of melt polymerization method. Afirst attempt to prepare isosorbide polycarbonate by melttransesterification reaction with DPC was reported in 1967. Thepolycondensation was carried out without the use of catalyst at 221° C.and the pressure was reduced from atmospheric pressure to 1 mm Hg.(Great Britain Patent No. 1,079,686). A brown white powder containinghigher melting and cross-linked constituents was obtained. Furtherattempts to prepare copolycarbonates of isosorbide with BPA,4,4′-dihydroxydiphenyl sulfide, and 4,4′-dihydroxy biphenyl bycondensation with DPC at a temperature up to 200° C. using disodium saltof bisphenol A as transesterification catalyst was carried out andresulted in the formation of oligocarbonates. The phenylcarbonate endgroups of the oligocarbonates were hydrolyzed and polymerized byinterfacial polymerization to high molecular weight copolycarbonates.(German Patent No. OS 3,002,276). The melt polycondensation approach wasrepeated in 1981 (U.S. Pat. No. 4,506,066), wherein isosorbide wascondensed with DPC at 220° C. and a pale brown polymer along withinsoluble constituents was obtained. In this study, it was presumed thatduring melt polymerization conditions branching had occurred and leadsto the formation of insoluble inhomogeneous product. Thus, it wasconcluded that melt polycondensation is not suitable for the preparationof isosorbide homo- and copolycarbonates. Further evidence to this comesfrom the detailed polymerization work carried out by Kricheldorf et. al.(Macromolecules 1996, vol. 29, p. 8077). One-step polycondensation ofisosorbide diphenyl carbonate with various diphenols catalyzed by ZnOwas carried out. This study also led to the formation of product whichwas insoluble in all common solvents tested.

U.S. Pat. No. 7,138,479 disclosed an activated carbonate melt process tosynthesize isosorbide based copolycarbonate which had randomarrangements of structural units. However, the attempts to synthesizeisosorbide homopolycarbonate using this method only resulted inrelatively low molecular weight isosorbide carbonate homopolymer.Examples 1 and 2 in Table 2 of U.S. Pat. No. 7,138,479 disclosed Mwvalues (gel permeation chromatography, polystyrene standards) of 16,060g/mol and 20,678 g/mol, prepared using non-activated and activated meltpolymerization processes, respectively; however, such Mw values are notsufficiently high for practical use in most, if not all, commercialapplications.

SUMMARY OF THE INVENTION

There accordingly remains a need in the art for high molecular weightisosorbide polycarbonate homopolymers and copolymers, and thus anefficient method to produce high quality homopolycarbonates fromaliphatic diols, specifically isosorbide. The above-described and otherdeficiencies of the art are overcome by a method of making apolycarbonate polymer comprising isosorbide carbonate units, comprisingmelt reacting a dihydroxy compound comprising an isosorbide of thegeneral formula (2a):

and an activated carbonate, in the presence of a catalyst consistingessentially of a sodium salt capable of providing a hydroxide ion,wherein the polycarbonate polymer comprises greater than or equal to 50mol % isosorbide carbonate units, and wherein the polycarbonate polymerhas a Mw of greater than or equal to about 40,000 g/mol as determined bygel-permeation chromatography relative to polystyrene standards.

In another embodiment, a polycarbonate polymer comprises carbonate unitsderived from a dihydroxy compound comprising an isosorbide of generalformula (2a):

and an activated carbonate, wherein the polycarbonate polymer comprisesgreater than 50 mol % isosorbide-derived carbonate units, and whereinthe polycarbonate polymer has a Mw of greater than or equal to about40,000 g/mol as determined by gel-permeation chromatography relative topolystyrene standards.

In another embodiment, a method of making a polycarbonate copolymercomprising isosorbide carbonate units comprises melt reacting adihydroxy compound comprising an isosorbide of the general formula (2a):

a C₂₋₁₃ aliphatic dioic acid or derivative thereof, and an activatedcarbonate, in the presence of a catalyst consisting essentially of asodium salt capable of providing a hydroxide ion, wherein thepolycarbonate polymer comprises greater than or equal to 50 mol %isosorbide carbonate units, and wherein the polycarbonate polymer has aMw of greater than or equal to about 46,000 g/mol as determined bygel-permeation chromatography relative to polystyrene standards.

A description of the figures, which are meant to be exemplary and notlimiting, is provided below.

BRIEF DESCRIPTION OF THE FIGURES

The FIGURE is a superimposed diagrammatic plot of weight averagedmolecular weight (Mw) and hydroxide concentration versus time for thepolymerization of isosorbide and bis(methyl salicyl)carbonate in thepresence of both an alpha and beta catalyst.

The above described and other features are exemplified by the followingdetailed description.

DETAILED DESCRIPTION OF THE INVENTION

Described herein is a useful method for preparing aliphatic diol-basedpolycarbonates, particularly aliphatic diol-based polycarbonates withhigh levels of aliphatic diol monomer. Surprisingly, a high molecularweight (i.e., Mw greater than 40,000 g/mol as determined by gelpermeation chromatography calibrated to polystyrene standards) aliphaticdiol-based polycarbonate can be prepared by a melt-polymerization methodusing an activated carbonate source in the presence of a singlecatalyst. The molecular weight of the resulting polymer is significantlyhigher than can be achieved for a comparable polymer prepared in thepresence of the traditional two catalyst system of an alpha and betacatalyst. The aliphatic diol used is derived from a biologically-derivedsugar, and specifically, comprises one or more isomers of isosorbide.Such aliphatic diol-based polycarbonates as disclosed herein desirablyhave high molecular weights as disclosed above, and are advantageous inthat they derive from renewable, biologically-based feedstocks and assuch can have a favorable impact on the environment. Such aliphaticdiol-based polycarbonates have properties that are comparable with thoseof typical non-aliphatic diol-based polycarbonates, including impactstrength, transparency, surface properties, moldability, ductility, andthe like. In addition, the aliphatic diol-based polycarbonates disclosedherein have other advantageous properties, such as biodegradability,improved scratch resistance, impact strength, and transparency, and areparticularly useful in high use exterior applications.

As used herein, the term “polycarbonate” includes generallyhomopolycarbonates and copolycarbonates having repeating structuralcarbonate units of the formula (1):

wherein the R¹ groups are derived from a dihydroxy compound that can bealiphatic, aromatic, or a combination of these.

Specifically, as disclosed herein, the polycarbonates are aliphaticdiol-based polycarbonates in which the R¹ groups of carbonate units offormula (1) comprise aliphatic groups, and in particular fused cyclicalkyloxy groups, such as those based on fused furan ring structures.

Specifically, the aliphatic diol-based polycarbonate comprises aliphaticdiol-based carbonate units shown in formula (2):

The aliphatic diol-based carbonate units of formula (2) can be derivedfrom the corresponding aliphatic diol or mixture of isomers of thealiphatic diol. The stereochemistry for the aliphatic diol-basedcarbonate units of formula (2a) is not particularly limited.Specifically, the aliphatic diol is an isosorbide of the general formula(2a):

and is also known interchangeably as2,6-dioxabicyclo[3.3.0]octan-4,8-diol, 1,4:3,6-dianhydro-D-glucitol, and2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol. The stereochemistryfor the isosorbide of general formula (2a) is also not particularlylimited. These diols are prepared by the dehydration of thecorresponding hexitols. Hexitols are produced commercially from thecorresponding sugars (aldohexose). Aliphatic diols of formula (2a)include 1,4; 3,6-dianhydro-D glucitol, of formula (2b); 1,4;3,6-dianhydro-D mannitol, of formula (2c); and 1,4; 3,6-dianhydro-Liditol, of formula (2d), and combinations of two or more of theaforementioned diols.

In a specific embodiment, the diol of the formula (2b) is desirablebecause it is a rigid, chemically and thermally stable aliphatic diolthat can produce higher Tg copolymers than the other diols of formulas(2c) and (2d).

The polycarbonate, including the aliphatic diol-based polycarbonate asdisclosed herein, can further comprise units derived from a dihydroxycompound, such as for example a bisphenol, that differs from thealiphatic diol of formula (2a). In one embodiment, each R¹ group is adivalent aromatic group, for example derived from an aromatic dihydroxycompound of the formula (3):HO-A¹-Y¹-A²-OH  (3)wherein each of A¹ and A² is a monocyclic divalent arylene group, and Y¹is a single bond or a bridging group having one or two atoms thatseparate A¹ from A². In an exemplary embodiment, one atom separates A¹from A². In another embodiment, when each of A¹ and A² is phenylene, Y¹is para to each of the hydroxyl groups on the phenylenes. Illustrativenon-limiting examples of groups of this type are —O—, —S—, —S(O)—,—S(O)₂—, —C(O)—, methylene, cyclohexyl-methylene,2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene,cyclododecylidene, and adamantylidene. The bridging group Y¹ can be ahydrocarbon group or a saturated hydrocarbon group such as methylene,cyclohexylidene, or isopropylidene.

Included within the scope of formula (3) are bisphenol compounds ofgeneral formula (4):

wherein R^(a) and R^(b) each represent a halogen atom or a monovalenthydrocarbon group and can be the same or different; p and q are eachindependently integers of 0 to 4; and X^(a) represents a single bond orone of the groups of formulas (5a) or (5b):

wherein R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl,C₁₋₁₂ cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, and R^(e) is a divalent C₁₋₁₂ hydrocarbon group. Inparticular, R^(c) and R^(d) are each the same hydrogen or C₁₋₄ alkylgroup, specifically the same C₁₋₃ alkyl group, even more specifically,methyl.

In an embodiment, R^(c) and R^(d) taken together represent a C₃₋₂₀cyclic alkylene group or a heteroatom-containing C₃₋₂₀ cyclic alkylenegroup comprising carbon atoms and heteroatoms with a valency of two orgreater. These groups can be in the form of a single saturated orunsaturated ring, or a fused polycyclic ring system wherein the fusedrings are saturated, unsaturated, or aromatic. A specificheteroatom-containing cyclic alkylene group comprises at least oneheteroatom with a valency of 2 or greater, and at least two carbonatoms. Exemplary heteroatoms in the heteroatom-containing cyclicalkylene group include —O—, —S—, and —N(Z)—, where Z is a substituentgroup selected from hydrogen, hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, orC₁₋₁₂ acyl.

In a specific exemplary embodiment, X^(a) is a substituted C₃₋₁₈cycloalkylidene of the formula (6):

wherein each R^(r), R^(p), R^(q), and R^(t) is independently hydrogen,halogen, oxygen, or C₁₋₁₂ organic group; I is a direct bond, a carbon,or a divalent oxygen, sulfur, or —N(Z)— wherein Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 1or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with theproviso that at least two of R^(r), R^(p), R^(q), and R^(t) takentogether are a fused cycloaliphatic, aromatic, or heteroaromatic ring.It will be understood that where the fused ring is aromatic, the ring asshown in formula (6) will have an unsaturated carbon-carbon linkagewhere the ring is fused. When k is 1 and i is 0, the ring as shown informula (6) contains 4 carbon atoms, when k is 2, the ring as showncontains 5 carbon atoms, and when k is 3, the ring contains 6 carbonatoms. In one embodiment, two adjacent groups (e.g., R^(q) and R^(t)taken together) form an aromatic group, and in another embodiment, R^(q)and R^(t) taken together form one aromatic group and R^(r) and R^(p)taken together form a second aromatic group.

When k is 3 and i is 0, bisphenols containing substituted orunsubstituted cyclohexane units are used, for example bisphenols offormula (7):

wherein substituents R^(a′) and R^(b′) can be aliphatic or aromatic,straight chain, cyclic, bicyclic, branched, saturated, or unsaturated,and R^(g) is C₁₋₁₂ alkyl or halogen, r and s are independently integersfrom 0 to 4, and t is an integer of 0 to 10. It will be understood thathydrogen fills each valency when r is 0, s is 0, and t is 0. In oneembodiment, each R^(a′) and R^(b′) is independently C₁₋₁₂ alkyl. In aspecific embodiment, where r and/or s is 1 or greater, at least one ofeach of R^(a′) and R^(b′) are disposed meta to the cyclohexylidenebridging group. The substituents R^(a′) R^(b′), and R^(g) may, whencomprising an appropriate number of carbon atoms, be straight chain,cyclic, bicyclic, branched, saturated, or unsaturated. In a specificembodiment, R^(a′), R^(b′), and R^(g) are each C₁₋₄ alkyl, specificallymethyl. In still another embodiment, R^(a′), R^(b′), and R^(g) is a C₁₋₃alkyl, specifically methyl, r and s are 0 or 1, and t is 0 to 5,specifically 0 to 3. Useful cyclohexane-containing bisphenols of formula(7) where t is 3, r and s are 0, and R^(g) is methyl include, forexample those derived from the reaction product of two moles of a phenolwith one mole of a hydrogenated isophorone such as e.g.,3,3,5-trimethylcyclohexanone, are useful for making polycarbonatepolymers with high glass transition temperatures and high heatdistortion temperatures. Such isophorone-bridged, bisphenol-containingpolycarbonates, or a combination comprising at least one of theforegoing with other bisphenol polycarbonates, can be obtained fromBayer Co. under the APEC® trade name.

Some illustrative, non-limiting examples of suitable bisphenol compoundsinclude the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxy-3 methyl phenyl)cyclohexane1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantine,(alpha,alpha′-bis(4-hydroxyphenyl)toluene,bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorene,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, and the like, as well as combinations comprisingat least one of the foregoing dihydroxy aromatic compounds.

Specific examples of the types of bisphenol compounds represented byformula (2) include 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane(hereinafter “bisphenol A” or “BPA”), 2,2-bis(4-hydroxyphenyl)butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane,3,3-bis(4-hydroxyphenyl)phthalimidine,2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (“PPPBP”), and9,9-bis(4-hydroxyphenyl)fluorene. Combinations comprising at least oneof the foregoing dihydroxy aromatic compounds can also be used.

Small amounts of other types of diols can be present in the aliphaticdiol-based polycarbonate. For example, a small portion of R¹ can bederived from a dihydroxy aromatic compound of formula (8):

wherein each R^(f) is independently C₁₋₁₂ alkyl, or halogen, and u is 0to 4. It will be understood that R^(f) is hydrogen when u is 0.Typically, the halogen can be chlorine or bromine. In an embodiment,compounds of formula (8) in which the —OH groups are substituted meta toone another, and wherein R^(f) and u are as described above, are alsogenerally referred to herein as resorcinols. Examples of compounds thatcan be represented by the formula (8) include resorcinol (where u is 0),substituted resorcinol compounds such as 5-methyl resorcinol, 5-ethylresorcinol, 5-propyl resorcinol, 5-butyl resorcinol, 5-t-butylresorcinol, 5-phenyl resorcinol, 5-cumyl resorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromo resorcinol, or the like; catechol;hydroquinone; substituted hydroquinones such as 2-methyl hydroquinone,2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone,2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone,2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone,2,3,5,6-tetrafluoro hydroquinone, 2,3,5,6-tetrabromo hydroquinone, orthe like; or combinations comprising at least one of the foregoingcompounds.

“Polycarbonate” as used herein includes homopolycarbonates andcopolymers comprising different R¹ moieties in the carbonate (referredto herein as “copolycarbonates”). In one specific embodiment, thepolycarbonate is a linear homopolymer or copolymer comprising unitsderived from bisphenol A, in which each of A¹ and A² is p-phenylene andY¹ is isopropylidene in formula (3). More specifically, at least 60%,particularly at least 80% of the R¹ groups in the polycarbonate arederived from bisphenol A.

Various types of polycarbonates with branching groups are alsocontemplated as being useful, provided that such branching does notsignificantly adversely affect desired properties of the polycarbonate.Branched polycarbonate blocks can be prepared by adding a branchingagent during polymerization. These branching agents includepolyfunctional organic compounds containing at least three functionalgroups selected from hydroxyl, carboxyl, carboxylic anhydride,haloformyl, and mixtures of the foregoing functional groups. Specificexamples include trimellitic acid, trimellitic anhydride, trimellitictrichloride, tris-p-hydroxy phenyl ethane, isatin-bis-phenol,tris-phenol TC (1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene),tris-phenol PA (4(4(1,1-bis(p-hydroxyphenyl)-ethyl)alpha, alpha-dimethylbenzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid, andbenzophenone tetracarboxylic acid. The branching agents can be added ata level of about 0.05 to about 2.0 wt %. Mixtures comprising linearpolycarbonates and branched polycarbonates can be used.

The relative amount of each type of carbonate unit present in thealiphatic diol-based polycarbonate will depend on the desired propertiesof the copolymer, and are readily ascertainable by one of ordinary skillin the art without undue experimentation, using the guidance providedherein. In general, the aliphatic diol-based polycarbonate will comprise1 to 100 mol %, specifically 10 to 100 mol %, even more specifically 15to 100 mol % of aliphatic diol-based carbonate units of formula (2). Inone embodiment the aliphatic diol-based polycarbonate comprises greaterthan 50 mol %, specifically greater than 60 mol %, and more specificallygreater than 70 mol % of aliphatic diol-based carbonate units, based onthe total number of carbonate units in the aliphatic diol-basedpolycarbonate. In an embodiment, the aliphatic diol-based carbonateunits are derived from the aliphatic diol of formula (2). The aliphaticdiol-based polycarbonate can further comprise 0 to 50 mol %,specifically 0 to 40 mol %, even more specifically 0 to 30 mol % ofadditional carbonate units. In an embodiment, each of the additionalcarbonate units is derived from the dihydroxy aromatic compound offormula (3). In a specific embodiment, the aliphatic diol-basedpolycarbonate is a homopolymer consisting essentially of carbonate unitsderived from the aliphatic diol of formula (2). In another specificembodiment, the aliphatic diol-based polycarbonate is a copolymercomprising 60 to 99 mol %, specifically 65 to 95 mol %, morespecifically 70 to 90 mol %, of aliphatic diol-based carbonate units offormula (2). In an embodiment, the aliphatic diol-based polycarbonate isa copolymer of formula (9) comprising aliphatic diol-based carbonateunits of formula (2) and additional carbonate units of formula (1) thatare not identical to the carbonate units of formula (2):

wherein R¹ is as described above, and the molar percentage ratio ofcarbonate units x to y is 50:50 to 100:0, specifically 60:40 to 100:0,and more specifically 70:30 to 100:0.

Each of the foregoing mole percents for formula (9) is based on thetotal moles of aliphatic diol-based carbonate units of formula (1) andadditional carbonate units. In an embodiment, where the aliphaticdiol-based polycarbonate of formula (9) is derived from an aliphaticdiol-based dihydroxy compound of formula (2a) and a dihydroxy aromaticcompound of formula (3), the mole percents are based on the total molesof aliphatic diol-based dihydroxy compound of formula (2) and dihydroxyaromatic compound of formula (3) used to manufacture the aliphaticdiol-based polycarbonate.

Other types of dihydroxy monomers, e.g., those of formula (9), can beused in amounts of up to 10 mol %, specifically up to 7 mol %, and evenmore specifically, up to 5 mol %. In an embodiment, the aliphaticdiol-based polycarbonate consists essentially of units derived from thealiphatic diol and a dihydroxy compound, wherein any dihydroxy compoundsused do not significantly adversely affect the desired properties of thealiphatic diol-based polycarbonate. In another specific embodiment, onlymonomers (i.e., diols) that fall within the scope of formulas (2) and(4) are used, that is, the aliphatic diol-based polycarbonate consistsof units derived from the aliphatic diol and dihydroxy aromaticcompounds.

Also as disclosed herein, polycarbonates including the aliphaticdiol-based polycarbonate can further include copolymers comprisingcarbonate units and other types of polymer units, such as ester units,polysiloxane units, and combinations comprising at least one ofhomopolycarbonates and copolycarbonates. A specific type ofpolycarbonate copolymer of this type is a polyester carbonate, alsoknown as a polyester-polycarbonate. Such copolymers further contain, inaddition to recurring carbonate chain units of the formula (1),carbonate units derived from oligomeric ester-containing dihydroxycompounds (also referred to herein as hydroxy end-capped oligomericarylate esters) comprising repeating units of formula (10):

wherein D is a divalent group derived from a dihydroxy compound, and maybe, for example, a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclic group, aC₆₋₂₀ aromatic group or a polyoxyalkylene group in which the alkylenegroups contain 2 to about 6 carbon atoms, specifically 2, 3, or 4 carbonatoms; and T divalent group derived from a dicarboxylic acid, and maybe, for example, a C₂₋₁₂₀ alkylene group, a C₆₋₂₀ alicyclic group, aC₆₋₂₀ allyl aromatic group, or a C₆₋₂₀ aromatic group.

In an embodiment, D is a C₂₋₃₀ alkylene group having a straight chain,branched chain, or cyclic (including polycyclic) structure. In anembodiment, D is a group derived from an aliphatic diol of formula (2a).In another embodiment, D is derived from an aromatic dihydroxy aromaticcompound of formula (4) above. In another embodiment, D is derived froma dihydroxy aromatic compound of formula (7) above.

Examples of aromatic dicarboxylic acids that may be used to prepare thepolyester units include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, and combinations comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexane dicarboxylic acid, or combinationsthereof. A specific dicarboxylic acid comprises a combination ofisophthalic acid and terephthalic acid wherein the weight ratio ofisophthalic acid to terephthalic acid is about 91:9 to about 2:98. Inanother specific embodiment, D is a C₂₋₆ alkylene group and T isp-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group,or a combination thereof. This class of polyester includes thepoly(allylene terephthalates).

The number of ester units in a polyester-polycarbonate is typicallygreater than or equal to 4, specifically greater than or equal to 5, andmore specifically greater than or equal to 8. Also in an embodiment, thenumber of ester units of formula (10) is less than or equal to 100,specifically less than or equal to 90, more specifically less than orequal to 70. It will be understood that the low and high endpoint valuesfor the number of ester units of formula (10) present are independentlycombinable. In a specific embodiment, the number of ester units offormula (10) in a polyester-polycarbonate can be 4 to 50, specifically 5to 30, more specifically 8 to 25, and still more specifically 10 to 20.The molar ratio of ester units to carbonate units in thepolyester-polycarbonate copolymers may vary broadly, for example 1:99 to99:1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25,depending on the desired properties of the final composition.

In an embodiment, the polyester unit of a polyester-polycarbonate may bederived from the reaction of a combination of isophthalic andterephthalic diacids (or derivatives thereof) with resorcinol. Inanother specific embodiment, the polyester unit of apolyester-polycarbonate is derived from the reaction of a combination ofisophthalic acid and terephthalic acid with bisphenol-A. In a specificembodiment, the carbonate units of a polyester-polycarbonate can bederived from aliphatic diols of formula (2a). Alternatively or inaddition, in an exemplary embodiment, the carbonate units can be derivedfrom resorcinol and/or bisphenol A. In another exemplary embodiment, thecarbonate units of the polyester-polycarbonate can be derived fromresorcinol and bisphenol A in a resulting molar ratio of resorcinolcarbonate units to bisphenol A carbonate unit of 1:99 to 99:1.

In a specific embodiment, the polyester unit of an aliphatic diol-basedpolyester polycarbonate is derived from the aliphatic diol of formula(2a) as described above, and a C₂₋₁₃ aliphatic dioic acid or derivativethereof from which T in formula (10) is derived. Such diacids are alsoreferred to generally as an alpha-omega diacids, and may be derived fromnatural sources, or from condensation of readily available feedstock.The dioic acid may be straight chain or branched, and may contain acyclic group. Exemplary diacids include oxalic acid, 1,4-propanedioicacid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid,1,10-decanedioic acid, and 1,12-dodecanedioic acid (DDDA). Dodecanedioicacid (the alpha-omega isomer, also referred to as the 1,12-isomer), acommonly available alpha-omega diacid include that derived fromoligomers of butadiene, is preferred. Such a C₁₂ aliphatic dioic acid(which comprises a C₁₀ alkylene chain connecting two carboxylic acid endgroups) is derived industrially from Ni-catalyzed cyclotrimerization ofbutadiene, hydrogenation to form cyclododecane, and is followed by ringopening oxidation to form the dodecanedioic acid. In an exemplaryembodiment, polyester units of formula (10) derive from the reactionproduct of isosorbide and DDDA (in which D corresponds to the bicyclo[3.3.0] ring structure of isosorbide as seen in formula (2a), and Tcorresponds to the C₁₀ alkylene chain that connects the two carboxyl endgroups of the DDDA), are prepared in situ during melt polymerization ofisosorbide and DDDA in the presence of a carbonate source, and inparticular an activated carbonate source. The resulting polyester unitcorresponds to a polyester unit of formula (10a):

wherein T¹ is a C₁₋₁₀ aliphatic group derived from the reaction productof the C₃₋₁₂ aliphatic dioic acid with the aliphatic diol of formula(2a), and z is an integer of greater than 1. In a specific embodiment,the polyester-polycarbonate is derived from aliphatic diol-basedcarbonate units of formula (2) and ester units of formula (10a), toprovide aliphatic diol-based polyester polycarbonates of formula (10b):

wherein T¹ is as described above, and the molar ratio of x to z is 50:50to 100:0, specifically 60:40 to 100:0, more specifically 70:30 to 100:0,still more specifically 80:20 to 100:0, and still yet more specifically85:15 to 100:0. In another specific embodiment, thepolyester-polycarbonate is derived from aliphatic diol-based carbonateunits of formula (2) ester units of formula (10a), and carbonate unitsof formula (1), to provide aliphatic diol-based polyester polycarbonatesof formula (10c):

wherein T¹ and R¹ are as described above, R¹ (of the carbonate unit offormula (1)) is not identical to the group corresponding to thealiphatic diol-based carbonate unit of formula (2), and the molar ratioof x, y, and z are respectively 50-100:0-30:0-20, specifically60-100:0-25:0-15, more specifically 70-100:0-20:0-10, and still morespecifically 80-100:0-15:0-5.

A polycarbonate can also include a polysiloxane-polycarbonate comprisingcarbonate units of formula (1) and polysiloxane blocks derived from asiloxane-containing dihydroxy compounds (also referred to herein as“hydroxyaryl end-capped polysiloxanes”) that contains diorganosiloxaneunits blocks of formula (11):

wherein each occurrence of R is same or different, and is a C₁₋₁₃monovalent organic group. For example, R can be a C₁-C₁₃ alkyl group,C₁-C₁₃ alkoxy group, C₂-C₁₃ alkenyl group, C₂-C₁₃ alkenyloxy group,C₃-C₆ cycloalkyl group, C₃-C₆ cycloalkoxy group, C₆-C₁₄ aryl group,C₆-C₁₀ aryloxy group, C₇-C₁₃ aralkyl group, C₇-C₁₃ aralkoxy group,C₇-C₁₃ alkylaryl group, or C₇-C₁₃ alkylaryloxy group. The foregoinggroups can be fully or partially halogenated with fluorine, chlorine,bromine, or iodine, or a combination thereof. In an embodiment, where atransparent aliphatic diol-based polycarbonate is desired, R does notcontain any halogen. Combinations of the foregoing R groups can be usedin the same aliphatic diol-based polycarbonate.

The value of E in formula (11) can vary widely depending on the type andrelative amount of each of the different units in the aliphaticdiol-based polycarbonate, the desired properties of the aliphaticdiol-based polycarbonate, and like considerations. Generally, E can havean average value of about 2 to about 1,000, specifically about 2 toabout 500, more specifically about 2 to about 100. In an embodiment, Ehas an average value of about 4 to about 90, specifically about 5 toabout 80, and more specifically about 10 to about 70. Where E is of alower value, e.g., less than about 40, it can be desirable to use arelatively larger amount of the units containing the polysiloxane.Conversely, where E is of a higher value, e.g., greater than about 40,it can be desirable to use a relatively lower amount of the unitscontaining the polysiloxane.

In one embodiment, the polysiloxane blocks are provided by repeatingstructural units of formula (12):

wherein E is as defined above; each R is the same or different, and isas defined above; and each Ar is the same or different, and is asubstituted or unsubstituted C₆-C₃₀ arylene group, wherein the bonds aredirectly connected to an aromatic moiety. Ar groups in formula (12) canbe derived from a C₆-C₃₀ dihydroxyarylene compound, for example adihydroxyarylene compound of formula (8) or (9) described in detailbelow. Combinations comprising at least one of the foregoingdihydroxyarylene compounds can also be used. Exemplary dihydroxyarylenecompounds are 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide),1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and1,1-bis(4-hydroxy-t-butylphenyl)propane, or a combination comprising atleast one of the foregoing dihydroxy compounds.

Polycarbonates comprising such units can be derived from thecorresponding dihydroxy compound of formula (12a):

wherein Ar and E are as described above. Compounds of formula (12a) canbe obtained by the reaction of a dihydroxyarylene compound with, forexample, an alpha, omega-bis-acetoxy-polydiorganosiloxane oligomer underphase transfer conditions. Compounds of formula (12a) can also beobtained from the condensation product of a dihydroxyarylene compound,with, for example, an alpha, omega bis-chloro-polydimethylsiloxaneoligomer in the presence of an acid scavenger.

In another embodiment, polydiorganosiloxane blocks comprises units offormula (13):

wherein R and E are as described above, and each R⁶ is independently adivalent C₁-C₃₀ organic group, and wherein the oligomerized polysiloxaneunit is the reaction residue of its corresponding dihydroxy compound.The polysiloxane blocks corresponding to formula (13) are derived fromthe corresponding dihydroxy compound (13a):

wherein R and E and R⁶ are as described for formula (13).

In a specific embodiment, the polydiorganosiloxane blocks are providedby repeating structural units of formula (14):

wherein R and E are as defined above. R⁷ in formula (14) is a divalentC₂-C₈ aliphatic group. Each M in formula (14) can be the same ordifferent, and is a halogen, cyano, nitro, C₁-C₈ alkylthio, C₁-C₈ allyl,C₁-C₈ alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxy group, C₃-C₈ cycloalkyl,C₃-C₈ cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy, C₇-C₁₂ aralkyl, C₇-C₁₂aralkoxy, C₇-C₁₂ alkylaryl, or C₇-C₁₂ alkylaryloxy, wherein each n isindependently 0, 1, 2, 3, or 4.

In one embodiment, M is bromo or chloro, an allyl group such as methyl,ethyl, or propyl, an alkoxy group such as methoxy, ethoxy, or propoxy,or an aryl group such as phenyl, chlorophenyl, or tolyl; R⁷ is adimethylene, trimethylene or tetramethylene group; and R is a C₁₋₈alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such asphenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or acombination of methyl and trifluoropropyl, or a combination of methyland phenyl. In still another embodiment, M is methoxy, n is one, R⁷ is adivalent C₁-C₃ aliphatic group, and R is methyl.

Polysiloxane-polycarbonates comprising units of formula (14) can bederived from the corresponding dihydroxy polydiorganosiloxane (14a):

wherein each of R, E, M, R⁷, and n are as described above. Suchdihydroxy polysiloxanes can be made by effecting a platinum-catalyzedaddition between a siloxane hydride of formula (15):

wherein R and E are as previously defined, and an aliphaticallyunsaturated monohydric phenol. Exemplary aliphatically unsaturatedmonohydric phenols included, for example, eugenol, 2-allylphenol,4-allyl-2-methylphenol, 4-allyl-2-phenylphenol, 4-allyl-2-bromophenol,4-allyl-2-t-butoxyphenol, 4-phenyl-2-phenylphenol,2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol,2-allyl-4-bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol,4-allylphenol, and 2-allyl-4,6-dimethylphenol. Combinations comprisingat least one of the foregoing can also be used.

In an embodiment, the polysiloxane polycarbonate can comprisepolysiloxane blocks derived from the corresponding dihydroxypolysiloxane compound, present in an amount of 0.15 to 30 wt %,specifically 0.5 to 25 wt %, and more specifically 1 to 20 wt % based onthe total weight of polysiloxane blocks and carbonate units. In aspecific embodiment, the polysiloxane blocks are present in an amount of1 to 10 wt %, specifically 2 to 9 wt %, and more specifically 3 to 8 wt%, based on the total weight of polysiloxane blocks and carbonate units.

Polysiloxane-polycarbonates further comprise carbonate units of formula(1) derived from a dihydroxy aromatic compound of formula (4). In anexemplary embodiment, the dihydroxy aromatic compound is bisphenol A. Inan embodiment, the carbonate units comprising thepolysiloxane-polycarbonate are present in an amount of 70 to 99.85 wt %,specifically 75 to 99.5, and more specifically 80 to 99 wt % based onthe total weight of polysiloxane blocks and carbonate units. In aspecific embodiment, the carbonate units are present in an amount of 90to 99 wt %, specifically 91 to 98 wt %, and more specifically 92 to 97wt %, based on the total weight of polysiloxane blocks and carbonateunits.

The polycarbonates, including the aliphatic diol-based polycarbonatesdisclosed herein, can have a weight average molecular weight (Mw) ofgreater than about 1,000. In an embodiment, the aliphatic diol-basedpolycarbonates can have an Mw of less than or equal to about 100,000g/mol. In an embodiment, the aliphatic diol-based polycarbonate has anMw of greater than or equal to about 40,000 g/mol, specifically greaterthan or equal to about 42,000 g/mol, more specifically greater than orequal to about 45,000 g/mol, and still more specifically greater thanabout 50,000 g/mol. In a specific embodiment, the aliphatic diol-basedpolycarbonate is an isosorbide-based polycarbonate homopolymer with anMw of greater than or equal to about 40,000 g/mol. In another specificembodiment, the aliphatic diol-based polycarbonate is anisosorbide-based polycarbonate copolymer with an Mw of greater than orequal to about 46,000 g/mol, specifically greater than or equal to about48,000 g/mol, more specifically greater than or equal to about 50,000g/mol, and still more specifically greater than or equal to about 51,000g/mol. In a specific embodiment, the isosorbide-based polycarbonatecopolymer is an isosorbide-based polyester-polycarbonate comprisingcarbonate units and ester units. In an embodiment, the aliphaticdiol-based polycarbonate (homo- or copolymer) has a number averagedmolecular weight (Mn) of greater than or equal to about 17,000 g/mol,specifically greater than or equal to about 18,000 g/mol, morespecifically greater than or equal to about 19,000 g/mol, and still morespecifically greater than about 20,000 g/mol. The polydispersity (Mw/Mn)for the aliphatic diol-based polycarbonate is less than or equal to 3,specifically less than or equal to 2.5, more specifically less than orequal to 2.2, and still more specifically less than or equal to 2.1. Inan embodiment, the aliphatic diol-based polycarbonate is anisosorbide-based polycarbonate homo- or copolymer with a polydispersityof less than 2.0, specifically less than or equal to 1.96, andspecifically less than or equal to 1.9. Molecular weight (Mw and Mn) asdescribed herein, and polydispersity as calculated therefrom, is asdetermined using gel permeation chromatography (GPC), using acrosslinked styrene-divinylbenzene column and calibrated to polystyrenestandards. GPC samples are prepared in a solvent such as methylenechloride or chloroform at a concentration of about 1 mg/ml, and areeluted at a flow rate of about 1.5 ml/min.

Polycarbonates, including the aliphatic diol-based polycarbonatesdisclosed herein, can have a melt volume ratio (MVR) of about 0.5 toabout 80, more specifically about 2 to about 40 cm³/10 minutes, measuredat 250° C. under a load of 5 kg according to ASTM D1238-04.

The aliphatic diol-based polycarbonates can further be manufactured tobe substantially transparent. In this case, the aliphatic diol-basedpolycarbonate can have a transparency of greater than or equal to 55%,specifically greater than or equal to 60%, more specifically greaterthan or equal to 70%, still more specifically greater than or equal to80%, and still more specifically greater than or equal to 90%, asmeasured using 3.2 mm plaques according to ASTM D1003-00. Alternatively,or in addition, the aliphatic diol-based polycarbonates can have a hazeof less than or equal to 15%, specifically less than or equal to 10%,and still more specifically less than or equal to 5%, as measured using3.2 mm thick plaques according to ASTM D1003-00. In a specificembodiment, the aliphatic diol-based polycarbonate is anisosorbide-based polycarbonate homo- or copolymer with a haze of lessthan about 5%, and more specifically less than or equal to 4%, and stillmore specifically less than or equal to 3%, as measured using 3.2 mmthick plaques according to ASTM D1003-00.

Polycarbonates can typically be manufactured using an interfacial phasetransfer process or melt polymerization. Although the reactionconditions for interfacial polymerization can vary, an exemplary processgenerally involves dissolving or dispersing a dihydric phenol reactantin aqueous caustic soda or potash, adding the resulting mixture to awater-immiscible solvent medium such as for example methylene chloride,and contacting the reactants with a carbonate precursor (such asphosgene) in the presence of a catalyst such as, for example,triethylamine or a phase transfer catalyst salt, under controlled pHconditions, e.g., about 8 to about 10.

However, as disclosed herein, the aliphatic-diol based polycarbonate isdesirably prepared by a melt polymerization process. Generally, in themelt polymerization process, polycarbonates are prepared by co-reacting,in a molten state, the dihydroxy reactant(s) and a diaryl carbonateester, such as diphenyl carbonate, in the presence of atransesterification catalyst. The reaction may be carried out in typicalpolymerization equipment, such as one or more continuously stirredreactors (CSTR's), plug flow reactors, wire wetting fall polymerizers,free fall polymerizers, wiped film polymerizers, BANBURY® mixers, singleor twin screw extruders, or combinations of the foregoing. Volatilemonohydric phenol is removed from the molten reactants by distillationand the polymer is isolated as a molten residue. A specifically usefulmelt process for making polycarbonates uses a diaryl carbonate esterhaving electron-withdrawing substituents on the aryls. Examples ofspecifically useful diaryl carbonate esters with electron withdrawingsubstituents include bis(4-nitrophenyl)carbonate,bis(2-chlorophenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(methylsalicyl)carbonate, bis(4-methylcarboxylphenyl)carbonate,bis(2-acetylphenyl)carboxylate, bis(4-acetylphenyl)carboxylate, or acombination comprising at least one of the foregoing.

The melt polymerization includes a transesterification catalystcomprising a first catalyst, also referred to herein as an alphacatalyst, comprising a metal cation and an anion. In an embodiment, thecation is an alkali or alkaline earth metal comprising Li, Na, K, Cs,Rb, Mg, Ca, Ba, Sr, or a combination comprising at least one of theforegoing. The anion is hydroxide (OH⁻), superoxide (O²⁻), thiolate(HS⁻), sulfide (S²⁻), a C₁₋₂₀ alkoxide, a C₆₋₂₀ aryloxide, a C₁₋₂₀carboxylate, a phosphate including biphosphate, a C₁₋₂₀ phosphonate, asulfate including bisulfate, sulfites including bisulfites andmetabisulfites, a C₁₋₂₀ sulfonate, a carbonate including bicarbonate, ora combination comprising at least one of the foregoing. Salts of anorganic acid comprising both alkaline earth metal ions and alkali metalions can also be used. Salts of organic acids useful as catalysts areillustrated by alkali metal and alkaline earth metal salts of formicacid, acetic acid, stearic acid and ethyelenediamine tetraacetic acid.The catalyst can also comprise the salt of a non-volatile inorganicacid. By “nonvolatile” it is meant that the referenced compounds have noappreciable vapor pressure at ambient temperature and pressure. Inparticular, these compounds are not volatile at temperatures at whichmelt polymerizations of polycarbonate are typically conducted. The saltsof nonvolatile acids are alkali metal salts of phosphites; alkalineearth metal salts of phosphites; alkali metal salts of phosphates; andalkaline earth metal salts of phosphates. In general transesterificationcatalysts can include as salts hydroxides such as lithium hydroxide,sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesiumhydroxide, calcium hydroxide, barium hydroxide, lithium formate, sodiumformate, potassium formate, cesium formate, lithium acetate, sodiumacetate, potassium acetate, lithium carbonate, sodium carbonate,potassium carbonate, lithium methoxide, sodium methoxide, potassiummethoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide,lithium phenoxide, sodium phenoxide, potassium phenoxide, sodiumsulfate, potassium sulfate, NaH₂PO₃, NaH₂PO₄, Na₂H₂PO₃, KH₂PO₄, CsH₂PO₄,Cs₂H₂PO₄, Na₂SO₃, Na₂S₂O₅, sodium mesylate, potassium mesylate, sodiumtosylate, potassium tosylate, magnesium disodium ethylenediaminetetraacetate (EDTA magnesium disodium salt), or a combination comprisingat least one of the foregoing. It will be understood that the foregoinglist is exemplary and should not be considered as limited thereto. In anembodiment, the transesterification catalyst is an alpha catalystconsisting essentially of an alkali metal salt. In a specificembodiment, the catalyst consists essentially of a sodium salt capableof providing a hydroxide ion upon exposure to moisture. In a morespecific embodiment, the transesterification catalyst consistsessentially of a sodium salt such as sodium oxide; sodium hydroxide;sodium bicarbonate; sodium carbonate; sodium alkoxides such as sodiummethoxide, sodium ethoxide, sodium isopropoxide, sodium t-butoxide,sodium phenolate, or the like, or a combination comprising at least oneof the foregoing. In a specific embodiment, the sodium salt can generatesodium hydroxide upon exposure to moisture, or moisture and elevatedtemperatures as encountered during reaction and/or extrusion. Anexemplary sodium salt for use as a transesterification catalyst issodium hydroxide.

The alpha catalyst can be used in amounts of up to 150 μmol, based onthe scale of the reaction. In an embodiment, the amount of alphacatalyst can be about 0.01 to about 30 μmol, specifically about 0.01 toabout 20 μmol, more specifically about 0.1 to about 10 μmol, morespecifically about 0.5 to about 9 μmol, and still more specificallyabout 1 to about 7 μmol, per mole of aliphatic diol and any otherdihydroxy compound present in the melt polymerization. In anotherembodiment, the alpha catalyst can be used in an amount of about 6 toabout 75 μmol in production scale batch processes. In anotherembodiment, the alpha catalyst can be used in an amount of about 75 to150 μmol in production scale continuous operations (i.e., those havingshorter residence times for the reactants). In addition, the minimumamount of alpha catalyst used can be adjusted according to the Nacontent of the reactants, where the number of equivalents of Na (andpresent in the form as a reactive salt such as, for example, NaOH,Na₂CO₃, NaHCO₃, or the like) can be additive to the number ofequivalents of alpha catalyst used, to provide a total alpha catalystcontent for the polymerization reaction. The Na content can be in anyreactant, but is in an embodiment contributed specifically by theisosorbide. In an embodiment, the total alpha catalyst is the sum of theequivalents of Na plus the number of equivalents of alpha catalyst. TheNa level in the reactants can about 0.4 to about 10 ppm based on weight,and can vary with the commercial source of the reactant.

In addition, a second transesterification catalyst, also referred toherein as a beta catalyst, may be included in the melt polymerizationprocess, provided that the inclusion of such a secondtransesterification catalyst does not significantly adversely affect thedesirable properties of the aliphatic diol-based polycarbonate.Exemplary transesterification catalysts may further include acombination of a phase transfer catalyst of formula (R³)₄Q⁺X above,wherein each R³ is the same or different, and is a C₁₋₁₀ alkyl group; Qis a nitrogen or phosphorus atom; and X is a halogen atom or a C₁₋₈alkoxy group or C₆₋₁₈ aryloxy group. Exemplary phase transfer catalystsalts include, for example, [CH₃(CH₂)₃]₄NX, [CH₃(CH₂)₃]₄PX,[CH₃(CH₂)₅]₄NX, [CH₃(CH₂)₆]₄NX, [CH₃(CH₂)₄]₄NX, CH₃[CH₃(CH₂)₃]₃NX, andCH₃[CH₃(CH₂)₂]₃NX, wherein X is Cl⁻, Br⁻, a C₁₋₈ alkoxy group or a C₆₋₁₈aryloxy group. Examples of such transesterification catalysts includetetrabutylammonium hydroxide, methyltributylammonium hydroxide,tetrabutylammonium acetate, tetrabutylphosphonium hydroxide,tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, or acombination comprising at least one of the foregoing. Other melttransesterification catalysts include alkaline earth metal salts oralkali metal salts. In some embodiments, where a beta catalyst isdesired, the beta catalyst can be present in a molar ratio, relative tothe alpha catalyst, of less than or equal to 10, specifically less thanor equal to 5, more specifically less than or equal to 1, and still morespecifically less than or equal to 0.5. In an embodiment, the meltpolymerization reaction disclosed herein uses only an alpha catalyst asdescribed hereinabove, and is substantially free of any beta catalyst.As defined herein, “substantially free of” can mean where the betacatalyst has been excluded from the melt polymerization reaction. In aspecific embodiment, the beta catalyst is present in an amount of lessthan about 10 ppm, specifically less than about 1 ppm, more specificallyless than or equal to about 0.1 ppm, and more specifically less than orequal to about 0.01 ppm, and even more specifically less than or equalto about 0.001 ppm, based on the total weight of all components used inthe melt polymerization reaction.

In an embodiment, where a melt process is used, a thermal stabilizer canbe added to the polymerization to mitigate or eliminate any potentialdegradation of the dihydroxy alkylene oxide compound during the hightemperatures (up to about 350° C. or higher) of the melt polymerization.It is known that isosorbide polymers are susceptible to thermaldegradation, and therefore inclusion of a thermal stabilizer can reducethe degree of decomposition of the isosorbide compound and therebyprovide a lower level of impurity and lead to higher batch-to-batchconsistency in the desired properties of the polycarbonate composition.

The use of a melt process employing an activated carbonate isparticularly preferred. As used herein, the term “activated carbonate”,also at times referred to as activated diarylcarbonate, is defined as adiarylcarbonate that is more reactive than diphenylcarbonate intransesterification reactions. In an embodiment, the activated carbonatehas a formula (16):

wherein Ar is a substituted C₆₋₃₀ aromatic group. In a specificembodiment, the activated carbonates have the formula (17):

wherein Q¹ and Q² are each independently an activating group present onA¹ and A² respectively, positioned ortho to the carbonate linkage; A¹and A² are each independently aromatic rings which can be the same ordifferent; “d” and “e” have a value of 0 to a maximum equivalent to thenumber of replaceable hydrogen groups substituted on the aromatic ringsA¹ and A² respectively, and the sum “d+e” is greater than or equal to 1;R¹ and R² are each independently a C₁₋₃₀ aliphatic group, a C₃₋₃₀cycloaliphatic group, a C_(5,-30) aromatic group, cyano, nitro orhalogen; “b” has a value of 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A¹ minus “d”; and “c” isa whole number from 0 to a maximum equivalent to the number ofreplaceable hydrogen atoms on the aromatic ring A² minus “e”. Thenumber, type and location of the R¹ or R² substituents on the aromaticring is not limited unless they deactivate the carbonate and lead to acarbonate, which is less reactive than diphenylcarbonate.

Non-limiting examples of suitable activating groups Q¹ and Q² include(alkoxycarbonyl)aryl groups, halogens, nitro groups, amide groups,sulfone groups, sulfoxide groups, or imine groups with structures shownbelow:

wherein X is halogen or nitro; M¹ and M² independently compriseN-dialkyl, N-alkylaryl, an aliphatic functionality or an aromaticfunctionality; and R³ is an aliphatic functionality or an aromaticfunctionality.

Specific non-limiting examples of activated carbonates includebis(o-methoxycarbonylphenyl)carbonate, bis(o-chlorophenyl)carbonate,bis(o-nitrophenyl)carbonate, bis(o-acetylphenyl)carbonate,bis(o-phenylketonephenyl)carbonate, bis(o-formylphenyl)carbonate.Unsymmetrical combinations of these structures where the type and numberof substitutions on A¹ and A² are different can also be used as thecarbonate precursor. In an embodiment, the activated carbonate is anester-substituted diarylcarbonate having the formula (18):

wherein R⁴ is independently at each occurrence a C₁₋₂₀ aliphatic group,a C₄₋₂₀ cycloaliphatic group, or a C₄₋₂₀ aromatic group, R⁵ isindependently at each occurrence a halogen atom, cyano group, nitrogroup, a C₁₋₂₀ aliphatic group, a C₄₋₂₀ cycloaliphatic group, or a C₄₋₂₀aromatic group and f is independently at each occurrence an integerhaving a value of 0 to 4. In one embodiment, at least one of thesubstituents —CO₂R⁴ is attached in an ortho position of formula (18).

Examples of specific ester-substituted diarylcarbonates include, but arenot limited to, bis(methylsalicyl)carbonate (CAS Registry No.82091-12-1) (also known as BMSC orbis(o-methoxycarbonylphenyl)carbonate), bis(ethylsalicyl)carbonate,bis(propylsalicyl)carbonate, bis(butylsalicyl)carbonate,bis(benzylsalicyl)carbonate, bis(methyl-4-chlorosalicyl)carbonate andthe like. In one embodiment, bis(methylsalicyl)carbonate is used as theactivated carbonate in melt polycarbonate synthesis due to its lowermolecular weight and higher vapor pressure.

Some non-limiting examples of non-activating groups which, when presentin an ortho position, would not be expected to result in activatedcarbonates are alkyl, cycloalkyl or cyano groups. Some specific andnon-limiting examples of non-activated carbonates arebis(o-methylphenyl)carbonate, bis(p-cumylphenyl)carbonate,bis(p-(1,1,3,3-tetramethyl)butylphenyl)carbonate andbis(o-cyanophenyl)carbonate. Unsymmetrical combinations of thesestructures may also be used as non-activated carbonates.

An end-capping agent (also referred to as a chain-stopper) can be usedto limit molecular weight growth rate, and so control molecular weightin the polycarbonate. Exemplary chain-stoppers include certainmonophenolic compounds (i.e., phenyl compounds having a single freehydroxy group), monocarboxylic acid chlorides, and/ormonochloroformates. Phenolic chain-stoppers are exemplified by phenoland C₁-C₂₂ allyl-substituted phenols such as p-cumyl-phenol, resorcinolmonobenzoate, and p- and tertiary-butyl phenol, cresol, and monoethersof diphenols, such as p-methoxyphenol. Alkyl-substituted phenols withbranched chain alkyl substituents having 8 to 9 carbon atoms can bespecifically mentioned. Certain monophenolic UV absorbers can also beused as a capping agent, for example4-substituted-2-hydroxybenzophenones and their derivatives, arylsalicylates, monoesters of diphenols such as resorcinol monobenzoate,2-(2-hydroxyaryl)-benzotriazoles and their derivatives,2-(2-hydroxyaryl)-1,3,5-triazines and their derivatives, and the like.Endgroups can derive from the carbonyl source as well as any addedend-capping groups. Thus, in an embodiment, a polycarbonate can comprisea structural unit derived from the carbonyl source. In a furtherembodiment, the carbonyl source is derived from an activated ornon-activated carbonate. In a specific embodiment, where BMSC is used asthe carbonyl source, the endgroup is derived from and is a residue ofBMSC, having the structure of formula (18a):

In an embodiment, where the aliphatic diol-based polycarbonate isprepared using only an alpha catalyst, the endgroup derived from BMSC ispresent in an amount of less than or equal to 500 ppm, specifically lessthan or equal to 400 ppm, more specifically less than or equal to 300ppm, and still more specifically less than or equal to 200 ppm, based onthe weight of the polycarbonate.

Suitable monocarboxylic acid chlorides include monocyclic,mono-carboxylic acid chlorides such as benzoyl chloride, C₁-C₂₂allyl-substituted benzoyl chloride, toluoyl chloride,halogen-substituted benzoyl chloride, bromobenzoyl chloride, cinnamoylchloride, 4-nadimidobenzoyl chloride, and combinations thereof;polycyclic, mono-carboxylic acid chlorides such as trimellitic anhydridechloride, and naphthoyl chloride; and combinations of monocyclic andpolycyclic mono-carboxylic acid chlorides. Chlorides of aliphaticmonocarboxylic acids with less than or equal to about 22 carbon atomsare useful. Functionalized chlorides of aliphatic monocarboxylic acids,such as acryloyl chloride and methacryoyl chloride, are also useful.Also useful are monochloroformates including monocyclicmonochloroformates, such as phenyl chloroformate, C₁-C₂₂allyl-substituted phenyl chloroformate, p-cumyl phenyl chloroformate,toluene chloroformate, and combinations thereof.

The reactants for the polymerization reaction using an activatedaromatic carbonate can be charged into a reactor either in the solidform or in the molten form. Initial charging of reactants into a reactorand subsequent mixing of these materials under reactive conditions forpolymerization may be conducted in an inert gas atmosphere such as anitrogen atmosphere. The charging of one or more reactant may also bedone at a later stage of the polymerization reaction. Mixing of thereaction mixture is accomplished by any methods known in the art, suchas by stirring. Reactive conditions include time, temperature, pressureand other factors that affect polymerization of the reactants. Typicallythe activated aromatic carbonate is added at a mole ratio at about 0.8to about 1.3 and more preferably 0.9 to about 1.1 and all subrangesthere between, relative to the total moles of aromatic dihydroxycompound and aliphatic diol.

The melt polymerization reaction using an activated aromatic carbonateis conducted by subjecting the above reaction mixture to a series oftemperature-pressure-time protocols. In some embodiments, this involvesgradually raising the reaction temperature in stages while graduallylowering the pressure in stages. In one embodiment, the pressure isreduced from about atmospheric pressure at the start of the reaction toabout 0.01 millibar (1 Pa) or in another embodiment to 0.05 millibar (5Pa) in several steps as the reaction approaches completion. Thetemperature may be varied in a stepwise fashion beginning at atemperature of about the melting temperature of the reaction mixture andsubsequently increased to about 320° C. In one embodiment, the reactionmixture is heated from room temperature to about 150° C. Thepolymerization reaction starts at a temperature of about 150° C. toabout 220° C., then is increased to about 220° C. to about 250° C. andis then further increased to a temperature of about 250° C. to about320° C. and all subranges there between. The total reaction time isabout 30 minutes to about 200 minutes and all subranges there between.This procedure will generally ensure that the reactants react to givepolycarbonates with the desired molecular weight, glass transitiontemperature and physical properties. The reaction proceeds to build thepolycarbonate chain with production of ester-substituted alcoholby-product such as methyl salicylate. Efficient removal of theby-product may be achieved by different techniques such as reducing thepressure. Generally the pressure starts relatively high in the beginningof the reaction and is lowered progressively throughout the reaction andtemperature is raised throughout the reaction. Experimentation is neededto find the most efficient conditions for particular productionequipment.

The progress of the reaction may be monitored by measuring the meltviscosity or the weight average molecular weight of the reaction mixtureusing techniques known in the art such as gel permeation chromatography.These properties may be measured by taking discreet samples or may bemeasured on-line. After the desired melt viscosity and/or molecularweight is reached, the final polycarbonate product may be isolated fromthe reactor in a solid or molten form. It will be appreciated by aperson skilled in the art, that the method of making aliphatichomopolycarbonate and aliphatic-aromatic copolycarbonates as describedin the preceding sections may be made in a batch or a continuous processand the process disclosed herein is essentially preferably carried outin a solvent free mode. Reactors chosen should ideally be self-cleaningand should minimize any “hot spots.”However, vented extruders similar tothose that are commercially available may be used.

In one embodiment, the aliphatic homopolycarbonate andaliphatic-aromatic copolycarbonate may be prepared in an extruder in thepresence of one or more catalysts, wherein the carbonating agent is anactivated aromatic carbonate. The reactants for the polymerizationreaction can be fed to the extruder in powder or molten form. In oneembodiment, the reactants are dry blended prior to addition to theextruder. The extruder may be equipped with pressure reducing devices(e.g., vents), which serve to remove the activated phenol by-product andthus drive the polymerization reaction toward completion. The molecularweight of the polycarbonate product may be manipulated by controlling,among other factors, the feed rate of the reactants, the type ofextruder, the extruder screw design and configuration, the residencetime in the extruder, the reaction temperature and the pressure reducingtechniques present on the extruder. The molecular weight of thepolycarbonate product may also depend upon the structures of thereactants, such as, activated aromatic carbonate, aliphatic diol,dihydroxy aromatic compound, and the catalyst employed. Many differentscrew designs and extruder configurations are commercially availablethat use single screws, double screws, vents, back flight and forwardflight zones, seals, sidestreams and sizes. One skilled in the art mayhave to experiment to find the best designs using generally knownprincipals of commercial extruder design.

The aliphatic diol-based polycarbonates of isosorbide, includingcopolycarbonates with aromatic diols such as, e.g. bisphenol A (BPA), orwith dicarboxylic acids such as, in an exemplary embodiment dodecanedioic acid (DDDA), where the copolymer comprises isosorbide-diacid estergroups and isosorbide-based carbonate groups, and homopolycarbonates ofisosorbide made by the melt route using BMSC or DPC as the carbonatesource may discolor when exposed to high temperatures greater than 250°C. Residual catalyst in the polycarbonates may be a potentialcontributor to the discoloration. To arrest the effect of residualcatalyst in the polycarbonate in accelerating formation of color bodies,the residual catalyst may be quenched with calculated amounts ofphosphorus acid or n-butyl tosylate. The quenched polycarbonate onheating to high temperatures beyond 250° C. has higher resistance fordiscoloration. The type of quencher, mode of addition and dosage of eachquencher in relation to the catalyst dosage are critical for achievingthe optimum results. It was found that the best results were obtainedwhen phosphorus acid was used at 50 times (mole terms) the levels ofNaOH catalyst that was initially added in the reactor duringpolymerization.

Aliphatic diol-based polycarbonates, specifically isosorbide-basedpolycarbonates, can be prepared with relatively high molecular weightsas defined hereinabove where the amount of isosorbide is low as apercentage of the total number of moles of copolymerizable diols.However, it has been found previously that high Mw isosorbide-basedpolycarbonates cannot be prepared with high (greater than 50 mol %)percentages of isosorbide-based carbonate units. As disclosed herein,the problems of the prior art, that of making isosorbidehomopolycarbonate having high molecular weight, have been solved by theinventors hereof. Isosorbide homopolycarbonate of sufficiently highmolecular weight by both activated and non-activated melt polymerizationprocess can be prepared using the catalyst system disclosed herein. Acatalyst system consisting essentially of an alpha catalyst allowssynthesis of isosorbide homo- and copolycarbonates to a molecular weightabove 40,000 g/mol relative to polystyrene standards. This catalystsystem is applicable to melt polymerization processes using bothactivated carbonates (e.g., BMSC) and non-activated carbonates (e.g.,DPC), particularly to the activated (BMSC) process.

Typically, in the melt transesterification polymerization process formaking polycarbonate, the diol (aliphatic and/or aromatic) is condensedwith the carbonate source (e.g., BMSC or DPC) in the presence of acatalyst comprising: (a) an alpha catalyst selected from the groupconsisting of alkali metal salts and alkaline earth metal salts; and (b)a beta catalyst selected from the group consisting of quaternaryammonium compound and a quaternary phosphonium compounds. Surprisingly,it has been found that presence of a beta catalyst actually hinders themolecular weight building of isosorbide homopolymer. For example, in thepresence of the most commonly used beta catalysts, such astetramethylammonium hydroxide (TMAH) or tetrabutylphosphonium acetate(TBPA), the molecular weight of isosorbide homopolycarbonates was foundto be lower when compared to isosorbide homopolycarbonate prepared inthe absence of beta catalysts. Further, with the inclusion of increasingamounts of TMAH as a beta catalyst, the observed Mw of isosorbidehomopolycarbonate decreased. There is no literature disclosure of thisphenomenon for the production of isosorbide-based polycarbonates.Therefore, as disclosed herein, isosorbide polymers, i.e. homopolymersand copolymers, are prepared in the absence of the beta catalyst.Preferred catalysts for effecting the melt polymerization include theaforementioned alkali metal cation containing catalysts. In an exemplaryembodiment, sodium hydroxide is a useful catalyst. Isosorbide polymersso prepared have weight averaged molecular weights of greater than orequal to about 40,000 g/mol. In an embodiment, isosorbide-containingcopolymers can have weight averaged molecular weights greater than about45,000 g/mol. Polymer molecular weights are determined as discussedabove as determined by gel-permeation chromatography relative topolystyrene standards.

In addition to the aliphatic diol-based polycarbonates described above,thermoplastic compositions comprising combinations of the aliphaticdiol-based polycarbonate with other thermoplastic polymers that do notcomprise the aliphatic diol-based carbonate units of formula (2) can beprepared using, for example homopolycarbonates, other polycarbonatecopolymers (i.e., copolycarbonates) comprising different R¹ moieties inthe carbonate units of formula (1), polysiloxane-polycarbonates,polyester-carbonates (also referred to as a polyester-polycarbonates),and polyesters. These combinations can comprise 1 to 99 wt %,specifically 10 to 90, more specifically 20 to 80 wt % of the aliphaticdiol-based polycarbonate, with the remainder of the compositions beingother of the foregoing polymers, and/or additives as described below.

In addition to the aliphatic diol-based polycarbonate, the thermoplasticcomposition can include various additives ordinarily incorporated inresin compositions of this type, with the proviso that the additives areselected so as to not significantly adversely affect the desiredproperties of the thermoplastic composition. Combinations of additivescan be used. Such additives can be mixed at a suitable time during themixing of the components for forming the composition.

For example, the thermoplastic composition can further include as anadditive an impact modifier(s). Suitable impact modifiers are typicallyhigh molecular weight elastomeric materials derived from olefins,monovinyl aromatic monomers, acrylic and methacrylic acids and theirester derivatives, as well as conjugated dienes. The polymers formedfrom conjugated dienes can be fully or partially hydrogenated. Theelastomeric materials can be in the form of homopolymers or copolymers,including random, block, radial block, graft, and core-shell copolymers.Combinations of impact modifiers can be used.

A specific type of impact modifier is an elastomer-modified graftcopolymer comprising an elastomeric (i.e., rubbery) polymer substratehaving a Tg less than about 10° C., more specifically less than about−10° C., or more specifically about −40° to −80° C., and (ii) a rigidpolymeric superstrate grafted to the elastomeric polymer substrate.Materials suitable for use as the elastomeric phase include, forexample, conjugated diene rubbers, for example polybutadiene andpolyisoprene; copolymers of a conjugated diene with less than about 50wt % of a copolymerizable monomer, for example a monovinylic compoundsuch as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate;olefin rubbers such as ethylene propylene copolymers (EPR) orethylene-propylene-diene monomer rubbers (EPDM); ethylene-vinyl acetaterubbers; silicone rubbers; elastomeric C₁₋₈ alkyl(meth)acrylates;elastomeric copolymers of C₁₋₈ alkyl(meth)acrylates with butadieneand/or styrene; or combinations comprising at least one of the foregoingelastomers. Materials suitable for use as the rigid phase include, forexample, monovinyl aromatic monomers such as styrene and alpha-methylstyrene, and monovinylic monomers such as acrylonitrile, acrylic acid,methacrylic acid, and the C₁-C₆ esters of acrylic acid and methacrylicacid, specifically methyl methacrylate.

Specific exemplary elastomer-modified graft copolymers include thoseformed from styrene-butadiene-styrene (SBS), styrene-butadiene rubber(SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS(acrylonitrile-butadiene-styrene),acrylonitrile-ethylene-propylene-diene-styrene (AES),styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene(MBS), and styrene-acrylonitrile (SAN).

Where used, impact modifiers are generally present in amounts of up to30 parts by weight, specifically 1 to 30 parts by weight, based on 100parts by weight of aliphatic diol-based polycarbonate, additionalpolymer, and any impact modifier.

Possible fillers or reinforcing agents include, for example, silicatesand silica powders such as aluminum silicate (mullite), syntheticcalcium silicate, zirconium silicate, fused silica, crystalline silicagraphite, natural silica sand, or the like; boron powders such asboron-nitride powder, boron-silicate powders, or the like; oxides suchas TiO₂, aluminum oxide, magnesium oxide, or the like; calcium sulfate(as its anhydride, dihydrate or trihydrate); calcium carbonates such aschalk, limestone, marble, synthetic precipitated calcium carbonates, orthe like; talc, including fibrous, modular, needle shaped, lamellartalc, or the like; wollastonite; surface-treated wollastonite; glassspheres such as hollow and solid glass spheres, silicate spheres,cenospheres, aluminosilicate (armospheres), or the like; kaolin,including hard kaolin, soft kaolin, calcined kaolin, kaolin comprisingvarious coatings known in the art to facilitate compatibility with thepolymeric matrix resin, or the like; single crystal fibers or “whiskers”such as silicon carbide, alumina, boron carbide, iron, nickel, copper,or the like; fibers (including continuous and chopped fibers) such asasbestos, carbon fibers, glass fibers, such as E, A, C, ECR, R, S, D, orNE glasses, or the like; sulfides such as molybdenum sulfide, zincsulfide or the like; barium compounds such as barium titanate, bariumferrite, barium sulfate, heavy spar, or the like; metals and metaloxides such as particulate or fibrous aluminum, bronze, zinc, copper andnickel or the like; flaked fillers such as glass flakes, flaked siliconcarbide, aluminum diboride, aluminum flakes, steel flakes or the like;fibrous fillers, for example short inorganic fibers such as thosederived from blends comprising at least one of aluminum silicates,aluminum oxides, magnesium oxides, and calcium sulfate hemihydrate orthe like; natural fillers and reinforcements, such as wood flourobtained by pulverizing wood, fibrous products such as cellulose,cotton, sisal, jute, starch, cork flour, lignin, ground nut shells,corn, rice grain husks or the like; organic fillers such aspolytetrafluoroethylene; reinforcing organic fibrous fillers formed fromorganic polymers capable of forming fibers such as poly(ether ketone),polyimide, polybenzoxazole, poly(phenylene sulfide), polyesters,polyethylene, aromatic polyamides, aromatic polyimides, polyetherimides,polytetrafluoroethylene, acrylic resins, poly(vinyl alcohol) or thelike; as well as additional fillers and reinforcing agents such as mica,clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, tripoli,diatomaceous earth, carbon black, or the like, or combinationscomprising at least one of the foregoing fillers or reinforcing agents.

The fillers and reinforcing agents can be coated with a layer ofmetallic material to facilitate conductivity, or surface treated withsilanes to improve adhesion and dispersion with the polymeric matrixresin. In addition, the reinforcing fillers can be provided in the formof monofilament or multifilament fibers and can be used individually orin combination with other types of fiber, through, for example,co-weaving or core/sheath, side-by-side, orange-type or matrix andfibril constructions, or by other methods known to one skilled in theart of fiber manufacture. Exemplary co-woven structures include, forexample, glass fiber-carbon fiber, carbon fiber-aromatic polyimide(aramid) fiber, and aromatic polyimide fiberglass fiber or the like.Fibrous fillers can be supplied in the form of, for example, rovings,woven fibrous reinforcements, such as 0-90 degree fabrics or the like;non-woven fibrous reinforcements such as continuous strand mat, choppedstrand mat, tissues, papers and felts or the like; or three-dimensionalreinforcements such as braids. Fillers are generally used in amounts ofabout 1 to about 20 parts by weight, based on 100 parts by weight ofaliphatic diol-based polycarbonate, additional polymer, and any impactmodifier.

Exemplary antioxidant additives include, for example, organophosphitessuch as tris(nonyl phenyl)phosphite,tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite or the like; alkylated monophenols orpolyphenols; alkylated reaction products of polyphenols with dienes,such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane,or the like; butylated reaction products of para-cresol ordicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenylethers; alkylidene-bisphenols; benzyl compounds; esters ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydricor polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds such as distearylthiopropionate, dilaurylthiopropionate,ditridecylthiodipropionate,octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionateor the like; amides ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the like, orcombinations comprising at least one of the foregoing antioxidants.Antioxidants are generally used in amounts of about 0.01 to about 0.1parts by weight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Exemplary heat stabilizer additives include, for example,organophosphites such as triphenyl phosphite,tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono- anddi-nonylphenyl)phosphite or the like; phosphonates such asdimethylbenzene phosphonate or the like, phosphates such as trimethylphosphate, or the like, or combinations comprising at least one of theforegoing heat stabilizers. Heat stabilizers are generally used inamounts of about 0.01 to about 0.1 parts by weight, based on 100 partsby weight of aliphatic diol-based polycarbonate, additional polymer, andany impact modifier.

Light stabilizers and/or ultraviolet light (UV) absorbing additives canalso be used. Exemplary light stabilizer additives include, for example,benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or the like, or combinations comprising at least one ofthe foregoing light stabilizers. Light stabilizers are generally used inamounts of about 0.01 to about 5 parts by weight, based on 100 parts byweight of aliphatic diol-based polycarbonate, additional polymer, andany impact modifier.

Exemplary UV absorbing additives include for example,hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;cyanoacrylates; oxanilides; benzoxazinones;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB®5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB® 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(CYASORB®1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORB® UV-3638);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(UVINUL® 3030); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with particle size less than or equal to about 100nanometers; or the like, or combinations comprising at least one of theforegoing UV absorbers. UV absorbers are generally used in amounts ofabout 0.01 to about 5 parts by weight, based on 100 parts by weight ofaliphatic diol-based polycarbonate, additional polymer, and any impactmodifier.

Plasticizers, lubricants, and/or mold release agents can also be used.There is considerable overlap among these types of materials, whichinclude, for example, phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl)phosphate of bisphenol-A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; esters, for example,fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate,stearyl stearate, pentaerythritol tetrastearate, and the like;combinations of methyl stearate and hydrophilic and hydrophobic nonionicsurfactants comprising polyethylene glycol polymers, polypropyleneglycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers,or a combination comprising at least one of the foregoing glycolpolymers, e.g., methyl stearate and polyethylene-polypropylene glycolcopolymer in a suitable solvent; waxes such as beeswax, montan wax,paraffin wax, or the like. Such materials are generally used in amountsof about 0.1 to about 1 parts by weight, based on 100 parts by weight ofaliphatic diol-based polycarbonate, additional polymer, and any impactmodifier.

The term “antistatic agent” refers to monomeric, oligomeric, orpolymeric materials that can be processed into polymer resins and/orsprayed onto materials or articles to improve conductive properties andoverall physical performance. Examples of monomeric antistatic agentsinclude glycerol monostearate, glycerol distearate, glyceroltristearate, ethoxylated amines, primary, secondary and tertiary amines,ethoxylated alcohols, alkyl sulfates, alkylarylsulfates,alkylphosphates, alkylaminesulfates, alkyl sulfonate salts such assodium stearyl sulfonate, sodium dodecylbenzenesulfonate or the like,quaternary ammonium salts, quaternary ammonium resins, imidazolinederivatives, sorbitan esters, ethanolamides, betaines, or the like, orcombinations comprising at least one of the foregoing monomericantistatic agents.

Exemplary polymeric antistatic agents include certain polyesteramidespolyether-polyamide (polyetheramide) block copolymers,polyetheresteramide block copolymers, polyetheresters, or polyurethanes,each containing polyalkylene glycol moieties polyalkylene oxide unitssuch as polyethylene glycol, polypropylene glycol, polytetramethyleneglycol, and the like. Such polymeric antistatic agents are commerciallyavailable, for example PELESTAT® 6321 (Sanyo) or PEBAX® MH1657(Atofina), IRGASTAT® P18 and IRGASTAT® P22 (Ciba-Geigy). Other polymericmaterials that can be used as antistatic agents are inherentlyconducting polymers such as polyaniline (commercially available asPANIPOL®EB from Panipol), polypyrrole and polythiophene (commerciallyavailable from Bayer), which retain some of their intrinsic conductivityafter melt processing at elevated temperatures. In one embodiment,carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or acombination comprising at least one of the foregoing can be used in apolymeric resin containing chemical antistatic agents to render thecomposition electrostatically dissipative. Antistatic agents aregenerally used in amounts of about 0.05 to about 0.5 parts by weight,based on 100 parts by weight of aliphatic diol-based polycarbonate,additional polymer, and any impact modifier.

Colorants such as pigment and/or dye additives can also be present.Useful pigments can include, for example, inorganic pigments such asmetal oxides and mixed metal oxides such as zinc oxide, titaniumdioxides, iron oxides, or the like; sulfides such as zinc sulfides, orthe like; aluminates; sodium sulfo-silicates sulfates, chromates, or thelike; carbon blacks; zinc ferrites; ultramarine blue; organic pigmentssuch as azos, di-azos, quinacridones, perylenes, naphthalenetetracarboxylic acids, flavanthrones, isoindolinones,tetrachloroisoindolinones, anthraquinones, enthrones, dioxazines,phthalocyanines, and azo lakes; Pigment Red 101, Pigment Red 122,Pigment Red 149, Pigment Red 177, Pigment Red 179, Pigment Red 202,Pigment Violet 29, Pigment Blue 15, Pigment Blue 60, Pigment Green 7,Pigment Yellow 119, Pigment Yellow 147, Pigment Yellow 150, and PigmentBrown 24; or combinations comprising at least one of the foregoingpigments. Pigments are generally used in amounts of about 0.001 to about3 parts by weight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Exemplary dyes are generally organic materials and include, for example,coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile redor the like; lanthanide complexes; hydrocarbon and substitutedhydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; scintillationdyes such as oxazole or oxadiazole dyes; aryl- or heteroaryl-substitutedpoly(C₂₋₈) olefin dyes; carbocyanine dyes; indanthrone dyes;phthalocyanine dyes; oxazine dyes; carbostyryl dyes;napthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyldyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes;arylmethane dyes; azo dyes; indigoid dyes, thioindigoid dyes, diazoniumdyes; nitro dyes; quinone imine dyes; aminoketone dyes; tetrazoliumdyes; thiazole dyes; perylene dyes, perinone dyes;bis-benzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes;thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores suchas anti-stokes shift dyes which absorb in the near infrared wavelengthand emit in the visible wavelength, or the like; luminescent dyes suchas 7-amino-4-methylcoumarin;3-(2′-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3″″,5″″-tetra-t-butyl-p-quinquephenyl;2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1′-diethyl-2,2′-carbocyanine iodide;3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2;7-dimethylamino-4-methylquinolone-2;2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazoliumperchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate;2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole);rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, orthe like; or combinations comprising at least one of the foregoing dyes.Dyes are generally used in amounts of about 0.0001 to about 5 parts byweight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Where a foam is desired, useful blowing agents include for example, lowboiling halohydrocarbons and those that generate carbon dioxide; blowingagents that are solid at room temperature and when heated totemperatures higher than their decomposition temperature, generate gasessuch as nitrogen, carbon dioxide, and ammonia gas, such asazodicarbonamide, metal salts of azodicarbonamide, 4,4′oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammoniumcarbonate, or the like, or combinations comprising at least one of theforegoing blowing agents. Blowing agents are generally used in amountsof about 1 to about 20 parts by weight, based on 100 parts by weight ofaliphatic diol-based polycarbonate, additional polymer, and any impactmodifier.

Useful flame retardants include organic compounds that includephosphorus, bromine, and/or chlorine. Non-brominated and non-chlorinatedphosphorus-containing flame retardants can be preferred in certainapplications for regulatory reasons, for example organic phosphates andorganic compounds containing phosphorus-nitrogen bonds.

One type of exemplary organic phosphate is an aromatic phosphate of theformula (GO)₃P═O, wherein each G is independently an alkyl, cycloalkyl,aryl, alkylaryl, or aralkyl group, provided that at least one G is anaromatic group. Two of the G groups can be joined together to provide acyclic group, for example, diphenyl pentaerythritol diphosphate.Exemplary aromatic phosphates include, phenyl bis(dodecyl)phosphate,phenyl bis(neopentyl)phosphate, phenylbis(3,5,5′-trimethylhexyl)phosphate, ethyl diphenyl phosphate,2-ethylhexyl di(p-tolyl) phosphate, bis(2-ethylhexyl)p-tolyl phosphate,tritolyl phosphate, bis(2-ethylhexyl)phenyl phosphate,tri(nonylphenyl)phosphate, bis(dodecyl)p-tolyl phosphate, dibutyl phenylphosphate, 2-chloroethyl diphenyl phosphate, p-tolylbis(2,5,5′-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate,or the like. A specific aromatic phosphate is one in which each G isaromatic, for example, triphenyl phosphate, tricresyl phosphate,isopropylated triphenyl phosphate, and the like.

Di- or polyfunctional aromatic phosphorus-containing compounds are alsouseful, for example, compounds of the formulas below:

wherein each G¹ is independently a hydrocarbon having 1 to about 30carbon atoms; each G² is independently a hydrocarbon or hydrocarbonoxyhaving 1 to about 30 carbon atoms; each X is independently a bromine orchlorine; m is 0 to 4, and n is 1 to about 30. Exemplary di- orpolyfunctional aromatic phosphorus-containing compounds includeresorcinol tetraphenyl diphosphate (RDP), the bis(diphenyl) phosphate ofhydroquinone and the bis(diphenyl)phosphate of bisphenol-A,respectively, their oligomeric and polymeric counterparts, and the like.

Exemplary flame retardant compounds containing phosphorus-nitrogen bondsinclude phosphonitrilic chloride, phosphorus ester amides, phosphoricacid amides, phosphonic acid amides, phosphinic acid amides,tris(aziridinyl)phosphine oxide. When present, phosphorus-containingflame retardants are generally present in amounts of about 0.1 to about30 parts by weight, more specifically about 1 to about 20 parts byweight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Halogenated materials can also be used as flame retardants, for examplehalogenated compounds and resins of formula (19):

wherein R is an alkylene, alkylidene or cycloaliphatic linkage, e.g.,methylene, ethylene, propylene, isopropylene, isopropylidene, butylene,isobutylene, amylene, cyclohexylene, cyclopentylidene, or the like; oran oxygen ether, carbonyl, amine, or a sulfur containing linkage, e.g.,sulfide, sulfoxide, sulfone, or the like. R can also consist of two ormore alkylene or alkylidene linkages connected by such groups asaromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone, or thelike.

Ar and Ar′ in formula (19) are each independently mono- orpolycarbocyclic aromatic groups such as phenylene, biphenylene,terphenylene, naphthylene, or the like.

Y is an organic, inorganic, or organometallic radical, for example (a)halogen, e.g., chlorine, bromine, iodine, fluorine or (b) ether groupsof the general formula OB, wherein B is a monovalent hydrocarbon groupsimilar to X or (c) monovalent hydrocarbon groups of the typerepresented by R or (d) other substituents, e.g., nitro, cyano, and thelike, said substituents being essentially inert provided that there isgreater than or equal to one, specifically greater than or equal to two,halogen atoms per aryl nucleus.

When present, each X is independently a monovalent hydrocarbon group,for example an alkyl group such as methyl, ethyl, propyl, isopropyl,butyl, decyl, or the like; an aryl groups such as phenyl, naphthyl,biphenyl, xylyl, tolyl, or the like; and aralkyl group such as benzyl,ethylphenyl, or the like; a cycloaliphatic group such as cyclopentyl,cyclohexyl, or the like. The monovalent hydrocarbon group can itselfcontain inert substituents.

Each d is independently 1 to a maximum equivalent to the number ofreplaceable hydrogens substituted on the aromatic rings comprising Ar orAr′. Each e is independently 0 to a maximum equivalent to the number ofreplaceable hydrogens on R. Each a, b, and c is independently a wholenumber, including 0. When b is not 0, neither a nor c can be 0.Otherwise either a or c, but not both, can be 0. Where b is 0, thearomatic groups are joined by a direct carbon-carbon bond.

The hydroxyl and Y substituents on the aromatic groups, Ar and Ar′ canbe varied in the ortho, meta or para positions on the aromatic rings andthe groups can be in any possible geometric relationship with respect toone another.

Included within the scope of the above formula are bisphenols of whichthe following are representative: 2,2-bis-(3,5-dichlorophenyl)-propane;bis-(2-chlorophenyl)-methane; bis(2,6-dibromophenyl)-methane;1,1-bis-(4-iodophenyl)-ethane; 1,2-bis-(2,6-dichlorophenyl)-ethane;1,1-bis-(2-chloro-4-iodophenyl)ethane;1,1-bis-(2-chloro-4-methylphenyl)-ethane;1,1-bis-(3,5-dichlorophenyl)-ethane;2,2-bis-(3-phenyl-4-bromophenyl)-ethane;2,6-bis-(4,6-dichloronaphthyl)-propane;2,2-bis-(2,6-dichlorophenyl)-pentane;2,2-bis-(3,5-dibromophenyl)-hexane; bis-(4-chlorophenyl)-phenyl-methane;bis-(3,5-dichlorophenyl)-cyclohexylmethane;bis-(3-nitro-4-bromophenyl)-methane;bis-(4-hydroxy-2,6-dichloro-3-methoxyphenyl)-methane; and2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane 2,2bis-(3-bromo-4-hydroxyphenyl)-propane. Also included within the abovestructural formula are: 1,3-dichlorobenzene, 1,4-dibromobenzene,1,3-dichloro-4-hydroxybenzene, and biphenyls such as2,2′-dichlorobiphenyl, polybrominated 1,4-diphenoxybenzene,2,4′-dibromobiphenyl, and 2,4′-dichlorobiphenyl as well as decabromodiphenyl oxide, and the like.

Also useful are oligomeric and polymeric halogenated aromatic compounds,such as a copolycarbonate of bisphenol A and tetrabromobisphenol A and acarbonate precursor, e.g., phosgene. Metal synergists, e.g., antimonyoxide, can also be used with the flame retardant. When present, halogencontaining flame retardants are generally present in amounts of about 1to about 25 parts by weight, more specifically about 2 to about 20 partsby weight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Alternatively, the thermoplastic composition can be essentially free ofchlorine and bromine. Essentially free of chlorine and bromine as usedherein refers to materials produced without the intentional addition ofchlorine or bromine or chlorine or bromine containing materials. It isunderstood however that in facilities that process multiple products acertain amount of cross contamination can occur resulting in bromineand/or chlorine levels typically on the parts per million by weightscale. With this understanding it can be readily appreciated thatessentially free of bromine and chlorine can be defined as having abromine and/or chlorine content of less than or equal to about 100 partsper million by weight (ppm), less than or equal to about 75 ppm, or lessthan or equal to about 50 ppm. When this definition is applied to thefire retardant it is based on the total weight of the fire retardant.When this definition is applied to the thermoplastic composition it isbased on the total weight of the composition, excluding any filler.

Inorganic flame retardants can also be used, for example salts of C₁₋₁₆alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimarsalt), potassium perfluoroctane sulfonate, tetraethylammoniumperfluorohexane sulfonate, and potassium diphenylsulfone sulfonate, andthe like; salts formed by reacting for example an alkali metal oralkaline earth metal (for example lithium, sodium, potassium, magnesium,calcium and barium salts) and an inorganic acid complex salt, forexample, an oxo-anion, such as alkali metal and alkaline-earth metalsalts of carbonic acid, such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃or fluoro-anion complex such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄,K₂SiF₆, and/or Na₃AlF₆ or the like. When present, inorganic flameretardant salts are generally present in amounts of about 0.01 to about10 parts by weight, more specifically about 0.02 to about 1 parts byweight, based on 100 parts by weight of aliphatic diol-basedpolycarbonate, additional polymer, and any impact modifier.

Anti-drip agents can also be used in the composition, for example afibril forming or non-fibril forming fluoropolymer such aspolytetrafluoroethylene (PTFE). The anti-drip agent can be encapsulatedby a rigid copolymer as described above, for examplestyrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SAN is knownas TSAN. Encapsulated fluoropolymers can be made by polymerizing theencapsulating polymer in the presence of the fluoropolymer, for examplean aqueous dispersion. TSAN can provide significant advantages overPTFE, in that TSAN can be more readily dispersed in the composition. Anexemplary TSAN can comprise about 50 wt % PTFE and about 50 wt % SAN,based on the total weight of the encapsulated fluoropolymer. The SAN cancomprise, for example, about 75 wt % styrene and about 25 wt %acrylonitrile based on the total weight of the copolymer. Alternatively,the fluoropolymer can be pre-blended in some manner with a secondpolymer, such as for, example, an aromatic polycarbonate resin or SAN toform an agglomerated material for use as an anti-drip agent. Eithermethod can be used to produce an encapsulated fluoropolymer. Antidripagents are generally used in amounts of 0.1 to 10 percent by weight,based on 100 percent by weight of aliphatic diol-based polycarbonate,additional polymer, and any impact modifier.

Radiation stabilizers can also be present, specifically gamma-radiationstabilizers. Exemplary gamma-radiation stabilizers include alkylenepolyols such as ethylene glycol, propylene glycol, 1,3-propanediol,1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2-pentanediol,2,3-pentanediol, 1,4-pentanediol, 1,4-hexandiol, and the like;cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol,and the like; branched alkylenepolyols such as2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well asalkoxy-substituted cyclic or acyclic alkanes. Unsaturated alkenols arealso useful, examples of which include 4-methyl-4-penten-2-ol,3-methyl-pentene-3-ol, 2-methyl-4-penten-2-ol, 2,4-dimethyl-4-pene-2-ol,and 9-decen-1-ol, as well as tertiary alcohols that have at least onehydroxy substituted tertiary carbon, for example2-methyl-2,4-pentanediol (hexylene glycol), 2-phenyl-2-butanol,3-hydroxy-3-methyl-2-butanone, 2-phenyl-2-butanol, and the like, andcyclic tertiary alcohols such as 1-hydroxy-1-methyl-cyclohexane. Certainhydroxymethyl aromatic compounds that have hydroxy substitution on asaturated carbon attached to an unsaturated carbon in an aromatic ringcan also be used. The hydroxy-substituted saturated carbon can be amethylol group (—CH₂OH) or it can be a member of a more complexhydrocarbon group such as —CR⁴HOH or —CR₂ ⁴OH wherein R⁴ is a complex ora simple hydrocarbon. Specific hydroxy methyl aromatic compounds includebenzhydrol, 1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxy benzylalcohol and benzyl benzyl alcohol. 2-Methyl-2,4-pentanediol,polyethylene glycol, and polypropylene glycol are often used forgamma-radiation stabilization. Gamma-radiation stabilizing compounds aretypically used in amounts of 0.05 to 1 parts by weight based on 100parts by weight of aliphatic diol-based polycarbonate, additionalpolymer, and any impact modifier.

Thermoplastic compositions comprising the aliphatic diol-basedpolycarbonate can be manufactured by various methods. For example,powdered aliphatic diol-based polycarbonate, other polymer (if present),and/or other optional components are first blended, optionally withfillers in a HENSCHEL-Mixer® high speed mixer. Other low shearprocesses, including but not limited to hand mixing, can also accomplishthis blending. The blend is then fed into the throat of a twin-screwextruder via a hopper. Alternatively, at least one of the components canbe incorporated into the composition by feeding directly into theextruder at the throat and/or downstream through a sidestuffer.Additives can also be compounded into a masterbatch with a desiredpolymeric resin and fed into the extruder. The extruder is generallyoperated at a temperature higher than that necessary to cause thecomposition to flow. The extrudate is immediately quenched in a waterbatch and pelletized. The pellets, so prepared, when cutting theextrudate can be one-fourth inch long or less as desired. Such pelletscan be used for subsequent molding, shaping, or forming.

The process disclosed herein can be used to prepare aliphaticpolycarbonate and aliphatic-aromatic copolycarbonates having a weightaverage molecular weight (Mw) of greater than about 40,000 g/mol. Theglass transition temperature (Tg) of the aliphatic diol-basedpolycarbonates can be greater than or equal to about 140° C.,specifically greater than or equal to about 145° C., and morespecifically greater than or equal to about 150° C. In one embodimentthe glass transition temperature of the aliphatic diol-basedpolycarbonates can be greater than or equal to about 90° C. and lessthan about 130° C. In another embodiment the glass transitiontemperature of the aliphatic diol-based polycarbonates can be greaterthan or equal to about 100° C. and less than about 125° C. The numberaverage molecular weights (Mn) of the aliphatic-aromatic copolycarbonateis greater than about 17,000 g/mol. The homo and copolycarbonatesdisclosed herein may further exhibit lower Refractive Index (RI),transparency (high % transmission and low haze), higher scratchresistance and lower oxygen permeability compared to conventional BPAhomopolycarbonate. Furthermore, the disclosed homo and copolycarbonatesare also optically active where prepared using enantiomerically pure orenantiomerically enriched aliphatic diol (e.g., D-(+)-isosorbide, andthe like).

The homo and copolycarbonates may be used in making various articlesincluding, but not limited to a film, a sheet, an optical wave guide, adisplay device and a light emitting diode prism. Furthermore thepolycarbonates may further be used in making articles such as, exteriorbody panels and parts for outdoor vehicles and devices includingautomobiles, protected graphics such as signs, outdoor enclosures suchas telecommunication and electrical connection boxes, and constructionapplications such as roof sections, wall panels and glazing. Multilayerarticles made of the disclosed polycarbonates particularly includearticles which will be exposed to UV-light, whether natural orartificial, during their lifetimes, and most particularly outdoorarticles; i.e., those intended for outdoor use. Suitable articles areexemplified by automotive, truck, military vehicle, and motorcycleexterior and interior components, including panels, quarter panels,rocker panels, trim, fenders, doors, decklids, trunklids, hoods,bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillarappliques, cladding, body side moldings, wheel covers, hubcaps, doorhandles, spoilers, window frames, headlamp bezels, headlamps, taillamps, tail lamp housings, tail lamp bezels, license plate enclosures,roof racks, and running boards; enclosures, housings, panels, and partsfor outdoor vehicles and devices; enclosures for electrical andtelecommunication devices; outdoor furniture; aircraft components; boatsand marine equipment, including trim, enclosures, and housings; outboardmotor housings; depth finder housings, personal water-craft; jet-skis;pools; spas; hot-tubs; steps; step coverings; building and constructionapplications such as glazing, roofs, windows, floors, decorative windowfurnishings or treatments; treated glass covers for pictures, paintings,posters, and like display items; wall panels, and doors; protectedgraphics; outdoor and indoor signs; enclosures, housings, panels, andparts for automatic teller machines (ATM); enclosures, housings, panels,and parts for lawn and garden tractors, lawn mowers, and tools,including lawn and garden tools; window and door trim; sports equipmentand toys; enclosures, housings, panels, and parts for snowmobiles;recreational vehicle panels and components; playground equipment;articles made from plastic-wood combinations; golf course markers;utility pit covers; computer housings; desktop computer housings;portable computer housings; lap-top computer housings; palm-heldcomputer housings; monitor housings; printer housings; keyboards; FAXmachine housings; copier housings; telephone housings; mobile phonehousings; radio sender housings; radio receiver housings; lightfixtures; lighting appliances; network interface device housings;transformer housings; air conditioner housings; cladding or seating forpublic transportation; cladding or seating for trains, subways, orbuses; meter housings; antenna housings; cladding for satellite dishes;coated helmets and personal protective equipment; coated synthetic ornatural textiles; coated photographic film and photographic prints;coated painted articles; coated dyed articles; coated fluorescentarticles; coated foam articles; and like applications.

The aliphatic diol-based polycarbonates are further illustrated by thefollowing non-limiting examples.

Gel Permeation Chromatography (GPC) was used to determine the molecularweights (Mw and Mn, and polydispersity) of the aliphatic diol-based(isosorbide) polycarbonates. A crosslinked styrene-divinylbenzenemixed-bed column was used for the analysis. The column temperature wasmaintained at 30° C. The column was eluted with chloroform as eluent, ata flow rate of 1.00 ml per minute. The sample solution was prepared bydissolving the 20 milligrams (mg) of the isosorbide polycarbonate in 10ml of chloroform. 10 microliters (μl) of the sample solution wasinjected in the column and the sample was eluted over a total run timeof less than 2 hours. A calibration curve (i.e., a universal calibrationcurve) was constructed using polystyrene standards with narrowpolydispersity. Molecular weights are expressed as molecular weightsagainst polystyrene. A refractive index detector was used.

Method I. Exemplary Method of Making Isosorbide PolycarbonateHomopolymer by the Activated Melt Polymerization Process (IncludingAlpha And Beta Catalysts):

To a cylindrical polymerization reactor made of glass and having alength of 29 cm, outer diameter 3.8 cm and inner diameter 3.2 cm, werecharged: (a) isosorbide (13.162 g, 0.08826 mol) (available fromRoquette, with a typical sodium level of 7 to 11 ppm as determined byatomic absorption spectroscopy); (b) bis(methylsalicyl) carbonate (BMSC)(30.0 g, 0.09090 mol); (c) NaOH (4.5×10⁻⁶ moles per mole of isosorbideand (d) tetramethylammonium hydroxide (1.00×10⁻⁴ moles per mole ofisosorbide). The atmosphere inside the reactor was then evacuated usinga vacuum source to a pressure of less than 1 millibar, and purged withnitrogen. This cycle was repeated 3 times after which the contents ofthe reactor were heated to melt the monomer mixture. Finally thepressure inside the reactor was raised to atmospheric pressure bynitrogen. Then, the reaction was heated over about 10 to 15 minutes to150° C. to melt the reactants, and held at temperature followed bytemperature/pressure increase/decrease according to the followingtemperature/pressure profile: (1) 150° C., 1 atmosphere for 10 minutes;(2) 180° C., 1 atmosphere, 10 minutes; (3) 200° C., 1 atmosphere, 5minutes; (4) 200° C., 500 millibar, 10 minutes; (5) 220° C., 100millibar, 15 minutes; (6) 270° C. at less than 1 millibar, 20 minutes.After allowing the reaction to proceed under these conditions, thepressure inside the reactor was brought to atmospheric pressure undernitrogen and the reactor was vented to relieve any excess pressure.Product isolation was accomplished by opening the drain nut at thebottom of the reactor, collecting the molten material, and allowing itto cool. M_(w)=<40,000 g/mol (GPC, PS standards); T_(g)=159-169° C.

Method II. Exemplary Method of Making High Molecular Weight IsosorbidePolycarbonate Homopolymer by the Activated Melt Polymerization Process(Alpha Catalyst Only).

The isosorbide polymerization was performed according to the same methodas disclosed in Method I, except that only c.) NaOH was included in thereaction, and no addition of component d.) (tetramethylammoniumhydroxide) was made. M_(w)=>40,000 g/mol (GPC, PS standards);T_(g)=159-160° C.

Method IIIa and IIIb. Exemplary Method of Making High Molecular WeightIsosorbide Polycarbonate Homopolymer by the Non-Activated MeltPolymerization Process (Alpha/Beta or Alpha Catalyst Only).

The isosorbide polymerization was performed according to the same methodas disclosed in Method I (for Method IIIa) or Method II (Method IIIb),except that diphenyl carbonate (DPC) was used instead of BMSC.Mw=<40,000 g/mol (GPC, PS standards); Tg=159-160° C.

Method IVa and IVb. Exemplary Method of Making High Molecular WeightIsosorbide-DDDA Polycarbonate Copolymer by the Non-Activated MeltPolymerization Process (Alpha/Beta or Alpha Catalyst Only).

The isosorbide polymerization was performed according to the same methodas disclosed in Method I (for Method IIIa) or Method II (Method IIIb),except that a 90:10 molar ratio of isosorbide to DDDA was used in placeof isosorbide only. Mw=>46,000 g/mol (GPC, PS standards).

EXAMPLES 1-5 AND COMPARATIVE EXAMPLES 1-34

Examples 1-5 and Comparative Examples 1-34 were prepared according tothe general method for activated melt polymerization synthesis describedbelow. Comparative Examples 27-30 were all prepared using anon-activated melt polymerization process. Alpha catalysts investigatedincluded sodium hydroxide (NaOH), sodium potassium hydrogen phosphate(NaKHPO₄), cesium hydroxide (CsOH), and sodium bisulfite (Na₂S₂O₅), andbeta catalysts used included tetramethylammonium hydroxide (TMAH) ortetrabutylphosphonium acetate (TBPA). The data are summarized in Table1, below.

TABLE 1 μmol μmol Mw Mn Comp. DAC Alpha (α) Beta (β) cat. (α) cat. (β)DAC/diol (g/mol) (g/mol) Mw/Mn CEx 1 100% iso BMSC NaOH TBPA 1.5 1001.015 14,129 8,118 1.74 CEx 2 100% iso BMSC NaOH TBPA 1.5 100 1.01012,778 7,257 1.76 CEx 3 100% iso BMSC NaOH TBPA 1.5 100 1.020 14,2188,159 1.74 CEx 4 100% iso BMSC NaOH TBPA 1.5 100 1.025 14,540 8,138 1.79CEx 5 100% iso BMSC NaOH TBPA 1.5 100 1.030 18,002 10,403 1.73 CEx 6100% iso BMSC NaOH TMAH 1.5 100 1.025 17,661 8,624 2.05 CEx 7 100% isoBMSC NaOH TMAH 1.5 100 1.03 23,340 12,064 1.93 CEx 8 100% iso BMSC NaOHTMAH 4.5 100 1.03 23,544 12,419 1.90 CEx 9 100% iso BMSC NaOH TMAH 1.565 1.03 26,178 13,963 1.87 CEx 10 100% iso BMSC — — 0 0 1.03 34,70920,828 1.67 Ex 1 100% iso BMSC NaOH — 1.5 0 1.03 42,843 22,162 1.93 Ex 2100% iso BMSC NaOH — 3 0 1.03 52,224 32,163 1.62 Ex 3 100% iso BMSC NaOH— 4.5 0 1.03 53,649 33,271 1.61 CEx 11 100% iso BMSC NaOH TMAH 1.5 251.03 35,772 21,575 1.66 CEx 12 100% iso BMSC NaOH TMAH 4.5 25 1.0339,783 20,866 1.91 CEx 13 100% iso BMSC NaHKPO₄ TBPA 20 100 1.015 18,1929,462 1.92 CEx 14 100% iso BMSC NaHKPO₄ TBPA 10 200 1.015 15,284 8,2981.84 CEx 15 100% iso BMSC NaHKPO₄ TBPA 10 400 1.015 13,350 7,253 1.84CEx 16 100% iso BMSC NaHKPO₄ TBPA 20 400 1.015 12,738 6,857 1.86 CEx 17100% iso BMSC NaHKPO₄ TBPA 20 100 1.015 20,795 10,730 1.94 CEx 18 100%iso BMSC NaHKPO₄ TBPA 50 100 1.015 28,477 15,510 1.84 CEx 19 100% isoBMSC NaHKPO₄ — 4.5 0 1.03 32,057 17,363 1.85 CEx 20 100% iso BMSCNaHKPO₄ TMAH 4.5 100 1.03 20,047 10,112 1.98 CEx 21 100% iso BMSC CsOH —4.5 0 1.03 31,751 16,355 1.94 CEx 22 100% iso BMSC CsOH TMAH 4.5 1001.03 24,541 12,419 1.98 CEx 23 100% iso BMSC CsOH — 4.5 0 1.03 32,15715,740 2.04 CEx 24 100% iso BMSC CsOH TMAH 4.5 100 1.03 21,315 9,8682.16 CEx 25 100% iso BMSC Na₂S₂O₅ — 4.5 0 1.03 38,228 22,496 1.70 CEx 26100% iso BMSC Na₂S₂O₅ TMAH 4.5 100 1.03 21,282 10,610 2.01 CEx 27 100%iso DPC NaOH — 4.5 0 1.050 31,549 17,042 1.85 CEx 28 100% iso DPC NaOHTMAH 4.5 100 1.050 23,652 15,305 1.55 CEx 29 100% iso DPC NaOH — 4.5 01.050 38,987 22,589 1.73 CEx 30 100% iso DPC NaOH TMAH 4.5 100 1.05029,880 15,470 1.93 Ex 4  90% iso/ BMSC NaOH — 4.5 0 1.03 53,777 32,2871.67  10% DDDA Ex 5  90% iso/ BMSC NaOH — 4.5 0 1.03 51,601 31,063 1.66 10% DDDA CEx 31  90% iso/ BMSC NaOH TMAH 4.5 100 1.03 33,207 17,1401.94  10% DDDA CEx 32  90% iso/ BMSC NaOH TMAH 4.5 25 1.03 45,223 26,4461.71  10% DDDA CEx 33  90% iso/ BMSC NaOH TMAH 1.5 100 1.03 35,15218,219 1.93  10% DDDA CEx 34  90% iso/ BMSC NaOH TMAH 1.5 25 1.03 41,87921,658 1.93  10% DDDA

As seen in the data in Table 1, isosorbide homopolymers prepared using abeta catalyst achieve a maximum weight averaged molecular weight of upto just under 40,000 (Comparative Example 12). However, in the absenceof a beta catalyst, the Mw for isosorbide homopolymer increases to42,800 or higher (Exs. 1-3). Use of alkali-based alpha catalysts such ascesium hydroxide (CExs. 21-24), or sodium potassium hydrogen phosphate(CExs. 13-20), or use of non-activated carbonate sources such as DPC(CExs. 27-30) result in lower molecular weights. In addition, polyestercopolymers can be prepared using the above method (IVa) (see Exs. 4 and5), to provide isosorbide-ester units in the polycarbonate (here, as theadduct with DDDA), where the polyester-polycarbonate copolymer hasdesirable Mw values of greater than 46,000 g/mol (GPC, PS standards).

By way of comparison, the progress of an activated carbonate meltpolymerization reaction to prepare isosorbide homopolymer (Mw versusreaction time) in the presence of a beta catalyst is shown graphicallyin the FIGURE. It can be seen that inclusion of the beta catalystinitially results in a small spike in molecular weigh (t=12 hours) whichoscillates until t equals about 17 hours at which time the BMSCconcentration is decreased as the hydroxide level increases.Simultaneously, Mw is observed to decrease. The delay is caused by theresidence time in the reactor system.

The singular forms “a,” “an,” and “the” include plural referents unlessthe context clearly dictates otherwise. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill in the art to which this inventionbelongs. The endpoints of all ranges directed to the same component orproperty are inclusive and independently combinable (e.g., ranges of“less than or equal to about 25 wt %, or, more specifically, about 5 wt% to about 20 wt %,” is inclusive of the endpoints and all intermediatevalues of the ranges of “about 5 wt % to about 25 wt %,” etc.). Thesuffix “(s)” as used herein is intended to include both the singular andthe plural of the term that it modifies, thereby including at least oneof that term (e.g., the colorant(s) includes at least one colorants).“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event occurs and instances where it does not. Asused herein, “combination” is inclusive of blends, mixtures, alloys,reaction products, and the like. All references are incorporated hereinby reference.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group.

As used herein, the term “hydrocarbyl” refers broadly to a substituentcomprising carbon and hydrogen, optional with at least one heteroatoms,for example, oxygen, nitrogen, halogen, or sulfur; “alkyl” refers to astraight or branched chain monovalent hydrocarbon group; “alkylene”refers to a straight or branched chain divalent hydrocarbon group;“alkylidene” refers to a straight or branched chain divalent hydrocarbongroup, with both valences on a single common carbon atom; “alkenyl”refers to a straight or branched chain monovalent hydrocarbon grouphaving at least two carbons joined by a carbon-carbon double bond;“cycloalkyl” refers to a non-aromatic monovalent monocyclic ormulticylic hydrocarbon group having at least three carbon atoms,“cycloalkenyl” refers to a non-aromatic cyclic divalent hydrocarbongroup having at least three carbon atoms, with at least one degree ofunsaturation; “aryl” refers to an aromatic monovalent group containingonly carbon in the aromatic ring or rings; “arylene” refers to anaromatic divalent group containing only carbon in the aromatic ring orrings; “alkylaryl” refers to an aryl group that has been substitutedwith an alkyl group as defined above, with 4-methylphenyl being anexemplary alkylaryl group; “arylalkyl” refers to an alkyl group that hasbeen substituted with an aryl group as defined above, with benzyl beingan exemplary arylalkyl group; “acyl” refers to an alkyl group as definedabove with the indicated number of carbon atoms attached through acarbonyl carbon bridge (—C(═O)—); “alkoxy” refers to an alkyl group asdefined above with the indicated number of carbon atoms attached throughan oxygen bridge (—O—); and “aryloxy” refers to an aryl group as definedabove with the indicated number of carbon atoms attached through anoxygen bridge (—O—). Where used, wavy bonds in structural formulas areincluded as generally in the art to show single bonds with unspecifiedstereochemistry.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions should not be deemed to be alimitation on the scope herein. Accordingly, various modifications,adaptations, and alternatives can occur to one skilled in the artwithout departing from the spirit and scope herein.

1. A method of making a polycarbonate polymer comprising isosorbide carbonate units, comprising melt reacting a dihydroxy compound comprising an isosorbide of the general formula (2a):

 and an activated carbonate, in the presence of a catalyst consisting essentially of a sodium salt capable of providing a hydroxide ion, wherein the polycarbonate polymer comprises greater than or equal to 50 mol% isosorbide carbonate units, and wherein the polycarbonate polymer has a Mw of greater than or equal to about 40,000 g/mol as determined by gel-permeation chromatography relative to polystyrene standards.
 2. The method of claim 1, wherein the isosorbide comprises formula (2b), formula (2c), formula (2d) or a combination comprising at least one of the foregoing:


3. The method of claim 1, wherein the activated carbonate has a formula(16):

wherein Ar is a substituted C₆₋₃₀ aromatic group.
 4. The method of claim 3, wherein the activated carbonate has formula (17):

wherein Q¹ and Q² are each independently an activating group present on A¹ and A² respectively, positioned ortho to the carbonate linkage; A¹ and A² are each independently aromatic rings which can be the same or different; “d” and “e” have a value of 0 to a maximum equivalent to the number of replaceable hydrogen groups substituted on the aromatic rings A¹ and A² respectively, and the sum “d +e” is greater than or equal to 1; R¹ and R² are each independently a C₁₋₃₀ aliphatic group, a C₃₋₃₀ cycloaliphatic group, a C_(5,-30) aromatic group, cyano, nitro or halogen; “b” has a value of 0 to a maximum equivalent to the number of replaceable hydrogen atoms on the aromatic ring A¹ minus “d” and “c” is a whole number from 0 to a maximum equivalent to the number of replaceable hydrogen atoms on the aromatic ring A² minus “e”.
 5. The method of claim 4, wherein the activated carbonate source comprises bis (methyl salicyl) carbonate.
 6. The method of claim 1, wherein the catalyst is present in an amount of 0.01 to 30 μmol, per mole of dihydroxy compound.
 7. The method of claim 1, where the sodium salt is sodium hydroxide.
 8. The method of claim 1, where the dihydroxy compound further comprises a dihydroxy compound that is not identical to isosorbide.
 9. The method of claim 8, wherein the dihydroxy compound is a dihydroxy aromatic compound.
 10. The method of claim 9, wherein the dihydroxy aromatic compound comprises a bisphenol of formula (4):

wherein R^(a) and R^(b) each independently represent halogen or C₁₋₁₂ alkyl; p and q are each independently integers of 0 to 4, and X^(a) is —O—, —S—, —S(O)—, S(O)₂—, or one of the groups of formula (5a) or (5b):

wherein R^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl, C₁₋₁₂ cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C⁷⁻¹² heteroarylalkyl, and R^(e) is a divalent C₁₋₁₂ hydrocarbon group.
 11. The method of claim 10 wherein R^(c) and R^(d) are methyl, and p and q are
 0. 12. The method of claim 1, wherein the method further comprises melt reacting a C₂₋₁₃ aliphatic dioic acid or derivative thereof with the isosorbide to form ester units, and wherein the polycarbonate polymer is a polyester-polycarbonate further comprising the ester units.
 13. The method of claim 12, wherein the aliphatic dioic acid is 1, 12-dodecanedioic acid.
 14. The method of claim 12, wherein the isosorbide polycarbonate polymer has a Mw of greater than or equal to 46,000 g/mol as determined by gel-permeation chromatography relative to polystyrene standards.
 15. The method of claim 1, wherein the dihydroxy compound consists essentially of isosorbide.
 16. A polycarbonate polymer, comprising carbonate units derived from a dihydroxy compound comprising an isosorbide of general formula (2a):

 and an activated carbonate, wherein the polycarbonate polymer comprises greater than 50 mol% isosorbide-derived carbonate units, and wherein the polycarbonate polymer has a Mw of greater than or equal to about 40,000 g/mol as determined by gel-permeation chromatography relative to polystyrene standards.
 17. The polycarbonate polymer of claim 14, wherein the polycarbonate polymer is a homopolymer consisting essentially of isosorbide-derived carbonate units.
 18. The polycarbonate polymer of claim 14, wherein the polycarbonate polymer further comprises additional carbonate units derived from a dihydroxy compound that is not identical to isosorbide, ester units derived from isosorbide and a C₃₋₁₂ aliphatic dioic acid or derivative, or a combination of these.
 19. The polycarbonate polymer of claim 16, wherein the polycarbonate polymer further comprises structural units derived from the activated aromatic carbonate.
 20. The composition according to claim 19, wherein the structural units derived from the activated aromatic carbonate are end groups comprising a residue of bis(methyl salicyl) carbonate.
 21. A method of making a polycarbonate copolymer comprising isosorbide carbonate units, comprising melt reacting a dihydroxy compound comprising an isosorbide of the general formula (2a):

a C₂₋₁₃ aliphatic dioic acid or derivative thereof, and an activated carbonate, in the presence of a catalyst consisting essentially of a sodium salt capable of providing a hydroxide ion, wherein the polycarbonate polymer comprises greater than or equal to 50 mol% isosorbide carbonate units, and wherein the polycarbonate polymer has a Mw of greater than or equal to about 46,000 g/mol as determined by gel-permeation chromatography relative to polystyrene standards.
 22. A polycarbonate polymer, prepared by the method of claim
 1. 23. A polycarbonate copolymer, prepared by the method of claim
 21. 24. A thermoplastic composition, comprising the polycarbonate polymer of claim 22 and an additive.
 25. An article, comprising the polycarbonate polymer of claim
 22. 